Benzhydryl derivatives

ABSTRACT

Benzhydryl derivatives of the formula I,  
                 
 
     where the index and the variables are as defined below:  
     X is oxygen or sulfur;  
     R 1 , R 3  are halogen, cyano, nitro, hydroxyl, mercapto, amino, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylcarbonyloxy, formyloxy, alkylthio, alkenylthio, alkynylthio, alkylamino, dialkylamino, alkylcarbonyl or formyl, where the carbon atoms in the radicals mentioned may be partially or fully halogenated;  
     R 2  is halogen, cyano, nitro, hydroxyl, mercapto, amino, alkyl, alkoxy, haloalkyl or haloalkoxy, where the groups R 2  may be different if n=2;  
     R 4  is alkyl, alkenyl or alkynyl, where the carbon atoms in these radicals may be unsubstituted or partially or fully halogenated;  
     R 5 , R 6  are hydroxyl, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy, alkenyloxy, haloalkoxy, haloalkenyloxy, cycloalkyl, cycloalkylalkyl, cycloalkoxy or cycloalkylalkoxy;  
     n is 0, 1 or 2;  
     processes for preparing the compounds I, compositions comprising them and their use for controlling phytopathogenic harmful fungi are described.

[0001] The invention relates to benzhydryl derivatives of the formula I,

[0002] where the index and the variables are as defined below:

[0003] X is oxygen or sulfur;

[0004] R¹, R³ are halogen, cyano, nitro, hydroxyl, mercapto, amino,

[0005] C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy, C₂-C₆-alkenyloxy, C₂-C₆-alkynyloxy, C₁-C₆-alkylcarbonyloxy, formyloxy, C₁-C₆-alkylthio, C₂-C₆-alkenylthio, C₂-C₆-alkynylthio, C₁-C₆-alkylamino, di-C₁-C₆-alkylamino, C₁-C₆-alkylcarbonyl or formyl, where the carbon atoms in the radicals mentioned may be partially or fully halogenated;

[0006] R² is halogen, cyano, nitro, hydroxyl, mercapto, amino, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C₆-haloalkoxy, where the groups R² may be different if n=2;

[0007] R⁴ is C₁-C₆-alkyl, C₂-C₆-alkenyl or C₂-C₆-alkynyl, where the carbon atoms in these radicals may be unsubstituted or partially or fully halogenated;

[0008] R⁵, R⁶ are hydroxyl, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₁-C₆-alkoxy, C₂-C₆-alkenyloxy, C₁-C₆-haloalkoxy, C₂-C₆-haloalkenyloxy, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyl-C₁-C₃-alkyl, C₃-C₈-cycloalkoxy or C₃-C₈-cycloalkyl-C₁-C₃-alkoxy;

[0009] n is 0, 1 or 2.

[0010] Additionally, the invention relates to processes for preparing the compounds I, to compositions comprising them and to the use of the compounds I for controlling phytopathogenic fungi.

[0011] In JP 08225474 various benzhydryl alcohols have been described as starting materials for pharmaceutics.

[0012] EP-A 461 079 discloses various benzhydryl alcohols having herbicidal action.

[0013] Benzhydryl alcohols having fungicidal action are already known, for example

[0014] (RS)-2,4′-difluoro-alpha-(1H-1,2,4-triazol-1-ylmethyl)benzhydryl alcohol (flutriafol; EP-A 015 756) or

[0015] (R,S)-2,4′-dichloro-alpha-(pyrimidin-5-yl)benzhydryl alcohol (fenarimol; GB 1 218 623). However, their action is not entirely satisfactory.

[0016] Benzophenones having fungicidal action are known from EP-A 727 141.

[0017] It is an object of the present invention to provide benzhydryl derivatives having a higher efficacy in the control of harmful fungi.

[0018] We have found that this object is achieved by the benzhydryl derivatives of the formula I. Furthermore, we have found processes for preparing the compounds I and compositions comprising them for controlling harmful fungi.

[0019] The compounds of the formula I differ from the benzhydryl alcohols disclosed in JP 08225474 by the substitution pattern on the phenyl rings.

[0020] The compounds of the formula I differ from the herbicidally active benzhydryl alcohols disclosed in EP-A 461 079 by the substituents of the phenyl rings, which substituents are fixed in positions 2, 2, 2′, 2′, 3′, 4 and 4′.

[0021] The compounds of the formula I are secondary alcohols or thiols, whereas the compounds disclosed in EP-A 015 756 and GB 1 218 623 are tertiary alcohols which furthermore differ from compounds of the formula I in the substitution pattern on the phenyl rings.

[0022] The compounds of the formula I differ from the fungicidally active benzophenones disclosed in EP-A 727 141 in that the keto group is replaced by an alcohol or thiol function, and by the substitution patterns on the phenyl rings.

[0023] In the definitions of the symbols given in the formulae above, collective terms were used which, in general, represent the following substituents:

[0024] Halogen: fluorine, chlorine, bromine or iodine, preferably chlorine or bromine;

[0025] Alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4 or 1 to 6 carbon atoms, for example C₁-C₆-alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;

[0026] Haloalkyl: straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as mentioned above), it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, for example C₁-C₂-haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;

[0027] Alkoxy: straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as mentioned above), which are attached to the phenyl ring via an oxygen atom (—O—);

[0028] Haloalkoxy: straight-chain or branched haloalkyl groups having 1 to 6 carbon atoms (as mentioned above) which are attached to the phenyl ring via an oxygen atom (—O—);

[0029] Alkylthio: straight-chain or branched alkyl groups having 1 to 6 or 1 to 4 carbon atoms (as mentioned above) which are attached to the phenyl ring via a sulfur atom (—S—);

[0030] Alkylamino: a straight-chain or branched alkyl group having 1 to 6 carbon atoms (as mentioned above) which is attached to the phenyl ring via an amino group (—NH—);

[0031] Dialkylamino: two independent straight-chain or branched alkyl groups having in each case 1 to 6 carbon atoms (as mentioned above) which are attached to the phenyl ring via a nitrogen atom;

[0032] Alkylcarbonyloxy: a straight-chain or branched alkyl group having 1 to 6 carbon atoms (as mentioned above) which is attached to the phenyl ring via a carbonyloxy group (—CO₂—);

[0033] Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 6 carbon atoms and a double bond in any position, for example C₂-C₆-alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;

[0034] Haloalkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 6 carbon atoms and a double bond in any position (as mentioned above), it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, in particular by fluorine, chlorine and bromine;

[0035] Alkenyloxy: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 6 carbon atoms and a double bond in any position which is not adjacent to the heteroatom (as mentioned above), which are attached to the phenyl ring via an oxygen atom (—O—);

[0036] Haloalkenyloxy: unsaturated, straight-chain or branched alkenyloxy groups having 3 to 6 carbon atoms (as mentioned above), it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, in particular by fluorine, chlorine and bromine;

[0037] Alkenylthio: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 6 carbon atoms and a double bond in any position which is not adjacent to the heteroatom (as mentioned above), which are attached to the phenyl ring via a sulfur atom (—S—);

[0038] Alkynyl: straight-chain or branched hydrocarbon groups having 2 to 6 carbon atoms and a triple bond in any position, for example C₂-C₆-alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;

[0039] Alkynyloxy: unsaturated, straight-chain or branched hydrocarbon radicals having 3 to 6 carbon atoms and a triple bond in any position which is not adjacent to the heteroatom (as mentioned above), which are attached to the skeleton via an oxygen atom (—O—);

[0040] Alkynylthio: unsaturated, straight-chain or branched hydrocarbon radicals having 3 to 6 carbon atoms and a triple bond in any position which is not adjacent to the heteroatom (as mentioned above), which are attached to the skeleton via a sulfur atom (—S—).

[0041] With respect to the intended use of the benzhydryl compounds of the formula I, the following meanings of the substituents are particularly preferred, in each case on their own or in combination:

[0042] Benzhydryl derivatives of the formula I as claimed in claim 1 where the variables are as defined below:

[0043] X is oxygen or sulfur;

[0044] R¹, R³ independently of one another are halogen, hydroxyl, mercapto, amino,

[0045] C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl, C₁-C₆-alkoxy, C₂-C₆-alkenyloxy, C₂-C₆-alkynyloxy, C₁-C₆-haloalkoxy, C₂-C₆-haloalkenyloxy, C₂-C₆-haloalkynyloxy, C₁-C₆-alkylcarbonyloxy, C₁-C₆-haloalkylcarbonyloxy, formyloxy, C₁-C₆-alkylthio, C₂-C₆-alkenylthio, C₂-C₆-alkynylthio, C₁-C₆-haloalkylthio, C₂-C₆-haloalkenylthio, C₂-C₆-haloalkynylthio, C₁-C₆-alkylamino, di-C₁-C₆-alkylamino, C₁-C₆-haloalkylamino, di-C₁-C₆-haloalkylamino, C₁-C6-alkylcarbonyl, C₁-C₆-haloalkylcarbonyl or formyl;

[0046] R² is halogen, hydroxyl, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C6-haloalkoxy, where the radicals R² may be different if n=2;

[0047] R⁴ is C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl or C₂-C₆-haloalkynyl;

[0048] R⁵, R⁶ independently of one another are hydroxyl, C₁-C₆-alkoxy, C₂-C₆-alkenyloxy, C₁-C₆-haloalkoxy or C₂-C₆-haloalkenyloxy;

[0049] n is 0, 1 or 2.

[0050] Particular preference is given to compounds I in which X is oxygen or sulfur;

[0051] R¹ and R³ independently of one another are halogen, hydroxyl, mercapto, amino, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy or C₁-C₆-alkylcarbonyl;

[0052] R² is halogen, hydroxyl, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy or C₁-C₆-haloalkoxy, where the radicals R² may be different if n=2;

[0053] R⁴ is methyl;

[0054] R⁵, R⁶ independently of one another are hydroxyl, C₁-C₆-alkoxy, C₂-C₆-alkenyloxy, C₁-C₆-haloalkoxy or C₂-C₆-haloalkenyloxy and

[0055] n is 0 or 1.

[0056] Especially preferred are compounds I in which X is oxygen.

[0057] Preference is furthermore given to compounds I in which R¹ and R³ independently of one another are halogen, hydroxyl, amino, mercapto, nitro, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylcarbonyloxy, C₁-C₆-haloalkylcarbonyloxy, C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, C₁-C₆-alkylcarbonyl or C₁-C₆-haloalkylcarbonyl. Here, particular mention may be made of: fluorine, chlorine, bromine or iodine, hydroxyl, mercapto, amino, methyl, ethyl, methoxy, ethoxy, methylcarbonyloxy, ethylcarbonyloxy, methylthio, ethylthio, trifluoromethyl, difluoromethoxy or chlorofluoromethoxy.

[0058] In addition, preference is given to compounds I in which R¹ and R³ independently of one another are halogen, hydroxyl, mercapto, amino, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy or C₁-C₆-haloalkoxy. Here, particular mention may be made of: fluorine, chlorine, bromine or iodine, hydroxyl, mercapto, amino, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy or chlorofluoromethoxy.

[0059] Particular preference is furthermore given to compounds I in which R¹ and R³ independently of one another are halogen, such as fluorine, chlorine, bromine or iodine, hydroxyl, C₁-C₆-alkyl, such as methyl or ethyl, C₁-C₆-alkoxy, such as methoxy or ethoxy, or C₁-C₆-alkylcarbonyloxy, such as methylcarbonyloxy or ethylcarbonyloxy.

[0060] In addition, particular preference is given to compounds I in which R¹ and R³ independently of one another are halogen, such as fluorine, chlorine, bromine or iodine, hydroxyl, C₁-C₆-alkyl, such as methyl or ethyl, or C₁-C₆-alkoxy, such as methoxy or ethoxy.

[0061] Very particular preference is given to compounds I in which R¹ and R³ independently of one another are halogen, such as chlorine or bromine, or C₁-C₆-alkyl, such as methyl or ethyl.

[0062] Likewise, very particular preference is given to compounds I in which R¹ and R³ independently of one another are hydroxyl, C₁-C₆-alkoxy, such as methoxy or ethoxy, or C₁-C₆-alkylcarbonyloxy, such as methylcarbonyloxy or ethylcarbonyloxy.

[0063] In addition, very particular preference is given to compounds I in which R¹ and R³ independently of one another are hydroxyl or C₁-C₆-alkoxy, such as methoxy or ethoxy.

[0064] Moreover, preference is also given to compounds I in which R² is halogen, hydroxyl, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy or C₁-C₆-haloalkoxy, where the groups R² may be different if n=2. Here, particular mention may be made of: fluorine, chlorine, bromine, iodine, methyl, ethyl, trifluoromethyl, difluoromethoxy, chlorofluoromethoxy.

[0065] Especially preferred are also compounds I in which R² is halogen, hydroxyl or C₁-C₆-alkoxy, such as methoxy or ethoxy.

[0066] Very particular preference is given to compounds I in which R² is halogen, in particular bromine or chlorine.

[0067] Moreover, particular preference is given to compounds I in which R⁴ is C₁-C₆-alkyl or C₁-C₆-haloalkyl. Here, particular mention may be made of: methyl, ethyl and trifluoromethyl.

[0068] Especially preferred are compounds I in which R⁴ is methyl.

[0069] Moreover, particular preference is given to compounds I in which R⁵ and R⁶ independently of one another are hydroxyl, C₁-C₆-alkoxy, C₂-C₆-alkenyloxy, C₁-C₆-haloalkoxy or C₂-C₆-haloalkenyloxy. Here, particular mention may be made of: hydroxyl, methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentoxy, hexoxy, propenyloxy, trifluoromethoxy, difluoromethoxy and chlorofluoromethoxy.

[0070] Particular preference is furthermore given to compounds I in which R⁵ and R⁶ independently of one another are hydroxyl or C₁-C₆-alkoxy, such as methoxy, ethoxy, propoxy, butoxy, pentoxy and hexoxy.

[0071] Very particular preference is given to compounds I in which R⁵ and R⁶ are methoxy.

[0072] In addition, particular preference is given to compounds I in which n is 0 or 1, very particularly preferably 1.

[0073] Very particular preference is given to compounds I in which R¹ and R³ independently of one another are fluorine, chlorine, bromine, iodine, hydroxyl, mercapto, methylthio, amino, methyl, ethyl, trifluoromethyl, methoxy, difluoromethoxy, fluorochloromethoxy, trifluoromethoxy, methylcarbonyloxy or ethylcarbonyloxy, R² is fluorine, chlorine, bromine, iodine, hydroxyl, methyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy or chlorofluoromethoxy, R⁴ is methyl, ethyl or trifluoromethyl, R⁵ and R⁶ independently of one another are hydroxyl, methoxy, ethoxy, n-propoxy, isopropoxy or n-butoxy and n is 0 or 1.

[0074] With respect to their use, particular preference is given to the compounds I-A compiled in the tables below. The groups mentioned in the tables for a substituent are furthermore in their own right, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituent in question.

[0075] Table 1

[0076] Compounds of formula I-A in which n is 0, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound corresponds in each case to one row of Table A

[0077] Table 2

[0078] Compounds of the formula I-A in which n is 1, R² is 3-methyl, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0079] Table 3

[0080] Compounds of the formula I-A in which n is 1, R² is 5-methyl, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0081] Table 4

[0082] Compounds of the formula I-A in which n is 1, R² is 3-trifluoromethyl, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0083] Table 5

[0084] Compounds of the formula I-A in which n is 1, R² is 5-trifluoromethyl, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0085] Table 6

[0086] Compounds of the formula I-A in which n is 1, R² is 3-hydroxyl, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0087] Table 7

[0088] Compounds of the formula I-A in which n is 1, R² is 5-hydroxyl, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0089] Table 8

[0090] Compounds of the formula I-A in which n is 1, R² is 3-methoxy, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0091] Table 9

[0092] Compounds of the formula I-A in which n is 1, R² is 5-methoxy, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0093] Table 10

[0094] Compounds of the formula I-A in which n is 1, R² is 3-ethoxy, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0095] Table 11

[0096] Compounds of the formula I-A in which n is 1, R² is 5-ethoxy, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0097] Table 12

[0098] Compounds of the formula I-A in which n is 1, R² is 3-difluoromethoxy, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0099] Table 13

[0100] Compounds of the formula I-A in which n is 1, R² is 5-difluoromethoxy, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0101] Table 14

[0102] Compounds of the formula I-A in which n is 1, R² is 3-chlorofluoromethoxy, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0103] Table 15

[0104] Compounds of the formula I-A in which n is 1, R² is 5-chlorofluoromethoxy, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0105] Table 16

[0106] Compounds of the formula I-A in which n is 1, R² is 3-fluorine, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0107] Table 17

[0108] Compounds of the formula I-A in which n is 1, R² is 5-fluorine, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0109] Table 18

[0110] Compounds of the formula I-A in which n is 1, R² is 3-chlorine, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0111] Table 19

[0112] Compounds of the formula I-A in which n is 1, R² is 5-chlorine, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0113] Table 20

[0114] Compounds of the formula I-A in which n is 1, R² is 3-bromine, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0115] Table 21

[0116] Compounds of the formula I-A in which n is 1, R² is 5-bromine, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0117] Table 22

[0118] Compounds of the formula I-A in which n is 1, R² is 3-iodine, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0119] Table 23

[0120] Compounds of the formula I-A in which n is 1, R² is 5-iodine, R⁴ is methyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0121] Table 24

[0122] Compounds of the formula I-A in which n is 0, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0123] Table 25

[0124] Compounds of the formula I-A in which n is 1, R² is 3-methyl, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0125] Table 26

[0126] Compounds of the formula I-A in which n is 1, R² is 5-methyl, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0127] Table 27

[0128] Compounds of the formula I-A in which n is 1, R² is 3-trifluoromethyl, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0129] Table 28

[0130] Compounds of the formula I-A in which n is 1, R² is 5-trifluoromethyl, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0131] Table 29

[0132] Compounds of the formula I-A in which n is 1, R² is 3-hydroxy, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0133] Table 30

[0134] Compounds of the formula I-A in which n is 1, R² is 5-hydroxy, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0135] Table 31

[0136] Compounds of the formula I-A in which n is 1, R² is 3-methoxy, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0137] Table 32

[0138] Compounds of the formula I-A in which n is 1, R² is 5-methoxy, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0139] Table 33

[0140] Compounds of the formula I-A in which n is 1, R² is 3-ethoxy, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0141] Table 34

[0142] Compounds of the formula I-A in which n is 1, R² is 5-ethoxy, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0143] Table 35

[0144] Compounds of the formula I-A in which n is 1, R² is 3-difluoromethoxy, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0145] Table 36

[0146] Compounds of the formula I-A in which n is 1, R² is 5-difluoromethoxy, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0147] Table 37

[0148] Compounds of the formula I-A in which n is 1, R² is 3-chlorofluoromethoxy, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0149] Table 38

[0150] Compounds of the formula I-A in which n is 1, R² is 5-chlorofluoromethoxy, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0151] Table 39

[0152] Compounds of the formula I-A in which n is 1, R² is 3-fluorine, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0153] Table 40

[0154] Compounds of the formula I-A in which n is 1, R² is 5-fluorine, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0155] Table 41

[0156] Compounds of the formula I-A in which n is 1, R² is 3-chlorine, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0157] Table 42

[0158] Compounds of the formula I-A in which n is 1, R² is 5-chlorine, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0159] Table 43

[0160] Compounds of the formula I-A in which n is 1, R² is 3-bromine, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0161] Table 44

[0162] Compounds of the formula I-A in which n is 1, R² is 5-bromine, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0163] Table 45

[0164] Compounds of the formula I-A in which n is 1, R² is 3-iodine, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0165] Table 46

[0166] Compounds of the formula I-A in which n is 1, R² is 5-iodine, R⁴ is ethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0167] Table 47

[0168] Compounds of the formula I-A in which n is 0, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0169] Table 48

[0170] Compounds of the formula I-A in which n is 1, R² is 3-methyl, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0171] Table 49

[0172] Compounds of the formula I-A in which n is 1, R² is 5-methyl, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0173] Table 50

[0174] Compounds of the formula I-A in which n is 1, R² is 3-trifluoromethyl, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0175] Table 51

[0176] Compounds of the formula I-A in which n is 1, R² is 5-trifluoromethyl, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0177] Table 52

[0178] Compounds of the formula I-A in which n is 1, R² is 3-hydroxyl, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0179] Table 53

[0180] Compounds of the formula I-A in which n is 1, R² is 5-hydroxy, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0181] Table 54

[0182] Compounds of the formula I-A in which n is 1, R² is 3-methoxy, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0183] Table 55

[0184] Compounds of the formula I-A in which n is 1, R² is 5-methoxy, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0185] Table 56

[0186] Compounds of the formula I-A in which n is 1, R² is 3-ethoxy, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0187] Table 57

[0188] Compounds of the formula I-A in which n is 1, R² is 5-ethoxy, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0189] Table 58

[0190] Compounds of the formula I-A in which n is 1, R² is 3-difluoromethoxy, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0191] Table 59

[0192] Compounds of the formula I-A in which n is 1, R² is 5-difluoromethoxy, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0193] Table 60

[0194] Compounds of the formula I-A in which n is 1, R² is 3-chlorofluoromethoxy, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0195] Table 61

[0196] Compounds of the formula I-A in which n is 1, R² is 5-chlorofluoromethoxy, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0197] Table 62

[0198] Compounds of the formula I-A in which n is 1, R² is 3-fluorine, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0199] Table 63

[0200] Compounds of the formula I-A in which n is 1, R² is 5-fluorine, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0201] Table 64

[0202] Compounds of the formula I-A in which n is 1, R² is 3-chlorine, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0203] Table 65

[0204] Compounds of the formula I-A in which n is 1, R² is 5-chlorine, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0205] Table 66

[0206] Compounds of the formula I-A in which n is 1, R² is 3-bromine, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0207] Table 67

[0208] Compounds of the formula I-A in which n is 1, R² is 5-bromine, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0209] Table 68

[0210] Compounds of the formula I-A in which n is 1, R² is 3-iodine, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0211] Table 69

[0212] Compounds of the formula I-A in which n is 1, R² is 5-iodine, R⁴ is trifluoromethyl and R⁶ is methoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0213] Table 70

[0214] Compounds of the formula I-A in which n is 0, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0215] Table 71

[0216] Compounds of the formula I-A in which n is 1, R² is 3-methyl, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0217] Table 72

[0218] Compounds of the formula I-A in which n is 1, R² is 5-methyl, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0219] Table 73

[0220] Compounds of the formula I-A in which n is 1, R² is 3-trifluoromethyl, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0221] Table 74

[0222] Compounds of the formula I-A in which n is 1, R² is 5-trifluoromethyl, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0223] Table 75

[0224] Compounds of the formula I-A in which n is 1, R² is 3-hydroxyl, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0225] Table 76

[0226] Compounds of the formula I-A in which n is 1, R² is 5-hydroxyl, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0227] Table 77

[0228] Compounds of the formula I-A in which n is 1, R² is 3-methoxy, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0229] Table 78

[0230] Compounds of the formula I-A in which n is 1, R² is 5-methoxy, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0231] Table 79

[0232] Compounds of the formula I-A in which n is 1, R² is 3-ethoxy, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0233] Table 80

[0234] Compounds of the formula I-A in which n is 1, R² is 5-ethoxy, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0235] Table 81

[0236] Compounds of the formula I-A in which n is 1, R² is 3-difluoromethoxy, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0237] Table 82

[0238] Compounds of the formula I-A in which n is 1, R² is 5-difluoromethoxy, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0239] Table 83

[0240] Compounds of the formula I-A in which n is 1, R² is 3-chlorofluoromethoxy, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0241] Table 84

[0242] Compounds of the formula I-A in which n is 1, R² is 5-chlorofluoromethoxy, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0243] Table 85

[0244] Compounds of the formula I-A in which n is 1, R² is 3-fluorine, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0245] Table 86

[0246] Compounds of the formula I-A in which n is 1, R² is 5-fluorine, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0247] Table 87

[0248] Compounds of the formula I-A in which n is 1, R² is 3-chlorine, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0249] Table 88

[0250] Compounds of the formula I-A in which n is 1, R² is 5-chlorine, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0251] Table 89

[0252] Compounds of the formula I-A in which n is 1, R² is 3-bromine, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0253] Table 90

[0254] Compounds of the formula I-A in which n is 1, R² is 5-bromine, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0255] Table 91

[0256] Compounds of the formula I-A in which n is 1, R² is 3-iodine, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0257] Table 92

[0258] Compounds of the formula I-A in which n is 1, R² is 5-iodine, R⁴ is methyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0259] Table 93

[0260] Compounds of the formula I-A in which n is 0, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0261] Table 94

[0262] Compounds of the formula I-A in which n is 1, R² is 3-methyl, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0263] Table 95

[0264] Compounds of the formula I-A in which n is 1, R² is 5-methyl, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0265] Table 96

[0266] Compounds of the formula I-A in which n is 1, R² is 3-trifluoromethyl, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0267] Table 97

[0268] Compounds of the formula I-A in which n is 1, R² is 5-trifluoromethoxy, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0269] Table 98

[0270] Compounds of the formula I-A in which n is 1, R² is 3-hydroxy, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹ , R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0271] Table 99

[0272] Compounds of the formula I-A in which n is 1, R² is 5-hydroxy, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0273] Table 100

[0274] Compounds of the formula I-A in which n is 1, R² is 3-methoxy, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0275] Table 101

[0276] Compounds of the formula I-A in which n is 1, R² is 5-methoxy, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0277] Table 102

[0278] Compounds of the formula I-A in which n is 1, R² is 3-ethoxy, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0279] Table 103

[0280] Compounds of the formula I-A in which n is 1, R² is 5-ethoxy, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0281] Table 104

[0282] Compounds of the formula I-A in which n is 1, R² is 3-difluoromethoxy, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0283] Table 105

[0284] Compounds of the formula I-A in which n is 1, R² is 5-difluoromethoxy, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0285] Table 106

[0286] Compounds of the formula I-A in which n is 1, R² is 3-chlorofluoromethoxy, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0287] Table 107

[0288] Compounds of the formula I-A in which n is 1, R² is 5-chlorofluoromethoxy, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹ , R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0289] Table 108

[0290] Compounds of the formula I-A in which n is 1, R² is 3-fluorine, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0291] Table 109

[0292] Compounds of the formula I-A in which n is 1, R² is 5-fluorine, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of 35 Table A, where R¹ is different from R³

[0293] Table 110

[0294] Compounds of the formula I-A in which n is 1, R² is 3-chlorine, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0295] Table 111

[0296] Compounds of the formula I-A in which n is 1, R² is 5-chlorine, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0297] Table 112

[0298] Compounds of the formula I-A in which n is 1, R² is 3-bromine, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0299] Table 113

[0300] Compounds of the formula I-A in which n is 1, R² is 5-bromine, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0301] Table 114

[0302] Compounds of the formula I-A in which n is 1, R² is 3-iodine, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0303] Table 115

[0304] Compounds of the formula I-A in which n is 1, R² is 5-iodine, R⁴ is ethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0305] Table 116

[0306] Compounds of the formula I-A in which n is 0, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0307] Table 117

[0308] Compounds of the formula I-A in which n is 1, R² is 3-methyl, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0309] Table 118

[0310] Compounds of the formula I-A in which n is 1, R² is 5-methyl, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0311] Table 119

[0312] Compounds of the formula I-A in which n is 1, R² is 3-trifluoromethyl, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0313] Table 120

[0314] Compounds of the formula I-A in which n is 1, R² is 5-trifluoromethyl, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0315] Table 121

[0316] Compounds of the formula I-A in which n is 1, R² is 3-hydroxy, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0317] Table 122

[0318] Compounds of the formula I-A in which n is 1, R² is 5-hydroxy, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹ , R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0319] Table 123

[0320] Compounds of the formula I-A in which n is 1, R² is 3-methoxy, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0321] Table 124

[0322] Compounds of the formula I-A in which n is 1, R² is 5-methoxy, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0323] Table 125

[0324] Compounds of the formula I-A in which n is 1, R² is 3-ethoxy, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0325] Table 126

[0326] Compounds of the formula I-A in which n is 1, R² is 5-ethoxy, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0327] Table 127

[0328] Compounds of the formula I-A in which n is 1, R² is 3-difluoromethoxy, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0329] Table 128

[0330] Compounds of the formula I-A in which n is 1, R² is 5-difluoromethoxy, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0331] Table 129

[0332] Compounds of the formula I-A in which n is 1, R² is 3-chlorofluoromethoxy, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0333] Table 130

[0334] Compounds of the formula I-A in which n is 1, R² is 5-chlorofluoromethoxy, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0335] Table 131

[0336] Compounds of the formula I-A in which n is 1, R² is 3-fluorine, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0337] Table 132

[0338] Compounds of the formula I-A in which n is 1, R² is 5-fluorine, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹ , R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0339] Table 133

[0340] Compounds of the formula I-A in which n is 1, R² is 3-chlorine, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0341] Table 134

[0342] Compounds of the formula I-A in which n is 1, R² is 5-chlorine, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹ , R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0343] Table 135

[0344] Compounds of the formula I-A in which n is 1, R² is 3-bromine, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0345] Table 136

[0346] Compounds of the formula I-A in which n is 1, R² is 5-bromine, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³

[0347] Table 137

[0348] Compounds of the formula I-A in which n is 1, R² is 3-iodine, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A

[0349] Table 138

[0350] Compounds of the formula I-A in which n is 1, R² is 5-iodine, R⁴ is trifluoromethyl and R⁶ is ethoxy and the combination of the radicals R¹, R³ and R⁵ for a compound in each case corresponds to one row of Table A, where R¹ is different from R³ TABLE A

I-A No. R¹ R³ R⁵ A-1 CH₃ CH₃ OH A-2 CH₂CH₃ CH₃ OH A-3 CF₃ CH₃ OH A-4 F CH₃ OH A-5 Cl CH₃ OH A-6 Br CH₃ OH A-7 I CH₃ OH A-8 OH CH₃ OH A-9 SH CH₃ OH A-10 SCH₃ CH₃ OH A-11 NH₂ CH₃ OH A-12 OCH₃ CH₃ OH A-13 OCHF₂ CH₃ OH A-14 OCHFCl CH₃ OH A-15 OCF₃ CH₃ OH A-16 OC(═O)CH₃ CH₃ OH A-17 OC(═O)CH₂CH₃ CH₃ OH A-18 CH₂CH₃ CH₂CH₃ OH A-19 CF₃ CH₂CH₃ OH A-20 F CH₂CH₃ OH A-21 Cl CH₂CH₃ OH A-22 Br CH₂CH₃ OH A-23 I CH₂CH₃ OH A-24 OH CH₂CH₃ OH A-25 SH CH₂CH₃ OH A-26 SCH₃ CH₂CH₃ OH A-27 NH₂ CH₂CH₃ OH A-28 OCH₃ CH₂CH₃ OH A-29 OCHF₂ CH₂CH₃ OH A-30 OCHFCl CH₂CH₃ OH A-31 OCF₃ CH₂CH₃ OH A-32 OC(═O)CH₃ CH₂CH₃ OH A-33 OC(═O)CH₂CH₃ CH₂CH₃ OH A-34 CF₃ CF₃ OH A-35 F CF₃ OH A-36 Cl CF₃ OH A-37 Br CF₃ OH A-38 I CF₃ OH A-39 OH CF₃ OH A-40 SH CF₃ OH A-41 SCH₃ CF₃ OH A-42 NH₂ CF₃ OH A-43 OCH₃ CF₃ OH A-44 OCHF₂ CF₃ OH A-45 OCHFCl CF₃ OH A-46 OCF₃ CF₃ OH A-47 OC(═O)CH₃ CF₃ OH A-48 OC(═O)CH₂CH₃ CF₃ OH A-49 F F OH A-50 Cl F OH A-51 Br F OH A-52 I F OH A-53 OH F OH A-54 SH F OH A-55 SCH₃ F OH A-56 NH₂ F OH A-57 OCH₃ F OH A-58 OCHF₂ F OH A-59 OCHFCl F OH A-60 OCF₃ F OH A-61 OC(═O)CH₃ F OH A-62 OC(═O)CH₂CH₃ F OH A-63 Cl Cl OH A-64 Br Cl OH A-65 I Cl OH A-66 OH Cl OH A-67 SH Cl OH A-68 SCH₃ Cl OH A-69 NH₂ Cl OH A-70 OCH₃ Cl OH A-71 OCHF₂ Cl OH A-72 OCHFCl Cl OH A-73 OCF₃ Cl OH A-74 OC(═O)CH₃ Cl OH A-75 OC(═O)CH₂CH₃ Cl OH A-76 Br Br OH A-77 I Br OH A-78 OH Br OH A-79 SH Br OH A-80 SCH₃ Br OH A-81 NH₂ Br OH A-82 OCH₃ Br OH A-83 OCHF₂ Br OH A-84 OCHFCl Br OH A-85 OCF₃ Br OH A-86 OC(═O)CH₃ Br OH A-87 OC(═O)CH₂CH₃ Br OH A-88 I I OH A-89 OH I OH A-90 SH I OH A-91 SCH₃ I OH A-92 NH₂ I OH A-93 OCH₃ I OH A-94 OCHF₂ I OH A-95 OCHFCl I OH A-96 OCF₃ I OH A-97 OC(═O)CH₃ I OH A-98 OC(═O)CH₂CH₃ I OH A-99 OH OH OH A-100 SH OH OH A-101 SCH₃ OH OH A-102 NH₂ OH OH A-103 OCH₃ OH OH A-104 OCHF₂ OH OH A-105 OCHFCl OH OH A-106 OCF₃ OH OH A-107 OC(═O)CH₃ OH OH A-108 OC(═O)CH₂CH₃ OH OH A-109 SH SH OH A-110 SCH₃ SH OH A-111 NH₂ SH OH A-112 OCH₃ SH OH A-113 OCHF₂ SH OH A-114 OCHFCl SH OH A-115 OCF₃ SH OH A-116 OC(═O)CH₃ SH OH A-117 OC(═O)CH₂CH₃ SH OH A-118 SCH₃ SCH₃ OH A-119 NH₂ SCH₃ OH A-120 OCH₃ SCH₃ OH A-121 OCHF₂ SCH₃ OH A-122 OCHFCl SCH₃ OH A-123 OCF₃ SCH₃ OH A-124 OC(═O)CH₃ SCH₃ OH A-125 OC(═O)CH₂CH₃ SCH₃ OH A-126 NH₂ NH₂ OH A-127 OCH₃ NH₂ OH A-128 OCHF₂ NH₂ OH A-129 OCHFCl NH₂ OH A-130 OCF₃ NH₂ OH A-131 OC(═O)CH₃ NH₂ OH A-132 OC(═O)CH₂CH₃ NH₂ OH A-133 OCH₃ OCH₃ OH A-134 OCHF₂ OCH₃ OH A-135 OCHFCl OCH₃ OH A-136 OCF₃ OCH₃ OH A-137 OC(═O)CH₃ OCH₃ OH A-138 OC(═O)CH₂CH₃ OCH₃ OH A-139 OCHF₂ OCHF₂ OH A-140 OCHFCl OCHF₂ OH A-141 OCF₃ OCHF₂ OH A-142 OC(═O)CH₃ OCHF₂ OH A-143 OC(═O)CH₂CH₃ OCHF₂ OH A-144 OCHFCl OCHFCl OH A-145 OCF₃ OCHFCl OH A-146 OC(═O)CH₃ OCHFCl OH A-147 OC(═O)CH₂CH₃ OCHFCl OH A-148 OCF₃ OCF₃ OH A-149 OC(═O)CH₃ OCF₃ OH A-150 OC(═O)CH₂CH₃ OCF₃ OH A-151 OC(═O)CH₃ OC(═O)CH₃ OH A-152 OC(═O)CH₂CH₃ OC(═O)CH₃ OH A-153 OC(═O)CH₂CH₃ OC(═O)CH₂CH₃ OH A-154 CH₃ CH₃ OCH₃ A-155 CH₂CH₃ CH₃ OCH₃ A-156 CF₃ CH₃ OCH₃ A-157 F CH₃ OCH₃ A-158 Cl CH₃ OCH₃ A-159 Br CH₃ OCH₃ A-160 I CH₃ OCH₃ A-161 OH CH₃ OCH₃ A-162 SH CH₃ OCH₃ A-163 SCH₃ CH₃ OCH₃ A-164 NH₂ CH₃ OCH₃ A-165 OCH₃ CH₃ OCH₃ A-166 OCHF₂ CH₃ OCH₃ A-167 OCHFCl CH₃ OCH₃ A-168 OCF₃ CH₃ OCH₃ A-169 OC(═O)CH₃ CH₃ OCH₃ A-170 OC(═O)CH₂CH₃ CH₃ OCH₃ A-171 CH₂CH₃ CH₂CH₃ OCH₃ A-172 CF₃ CH₂CH₃ OCH₃ A-173 F CH₂CH₃ OCH₃ A-174 Cl CH₂CH₃ OCH₃ A-175 Br CH₂CH₃ OCH₃ A-176 I CH₂CH₃ OCH₃ A-177 OH CH₂CH₃ OCH₃ A-178 SH CH₂CH₃ OCH₃ A-179 SCH₃ CH₂CH₃ OCH₃ A-180 NH₂ CH₂CH₃ OCH₃ A-181 OCH₃ CH₂CH₃ OCH₃ A-182 OCHF₂ CH₂CH₃ OCH₃ A-183 OCHFCl CH₂CH₃ OCH₃ A-184 OCF₃ CH₂CH₃ OCH₃ A-185 OC(═O)CH₃ CH₂CH₃ OCH₃ A-186 OC(═O)CH₂CH₃ CH₂CH₃ OCH₃ A-187 CF₃ CF₃ OCH₃ A-188 F CF₃ OCH₃ A-189 Cl CF₃ OCH₃ A-190 Br CF₃ OCH₃ A-191 I CF₃ OCH₃ A-192 OH CF₃ OCH₃ A-193 SH CF₃ OCH₃ A-194 SCH₃ CF₃ OCH₃ A-195 NH₂ CF₃ OCH₃ A-196 OCH₃ CF₃ OCH₃ A-197 OCHF₂ CF₃ OCH₃ A-198 OCHFCl CF₃ OCH₃ A-199 OCF₃ CF₃ OCH₃ A-200 OC(═O)CH₃ CF₃ OCH₃ A-201 OC(═O)CH₂CH₃ CF₃ OCH₃ A-202 F F OCH₃ A-203 Cl F OCH₃ A-204 Br F OCH₃ A-205 I F OCH₃ A-206 OH F OCH₃ A-207 SH F OCH₃ A-208 SCH₃ F OCH₃ A-209 NH₂ F OCH₃ A-210 OCH₃ F OCH₃ A-211 OCHF₂ F OCH₃ A-212 OCHFCl F OCH₃ A-213 OCF₃ F OCH₃ A-214 OC(═O)CH₃ F OCH₃ A-215 OC(═O)CH₂CH₃ F OCH₃ A-216 Cl Cl OCH₃ A-217 Br Cl OCH₃ A-218 I Cl OCH₃ A-219 OH Cl OCH₃ A-220 SH Cl OCH₃ A-221 SCH₃ Cl OCH₃ A-222 NH₂ Cl OCH₃ A-223 OCH₃ Cl OCH₃ A-224 OCHF₂ Cl OCH₃ A-225 OCHFCl Cl OCH₃ A-226 OCF₃ Cl OCH₃ A-227 OC(═O)CH₃ Cl OCH₃ A-228 OC(═O)CH₂CH₃ Cl OCH₃ A-229 Br Br OCH₃ A-230 I Br OCH₃ A-231 OH Br OCH₃ A-232 SH Br OCH₃ A-233 SCH₃ Br OCH₃ A-234 NH₂ Br OCH₃ A-235 OCH₃ Br OCH₃ A-236 OCHF₂ Br OCH₃ A-237 OCHFCl Br OCH₃ A-238 OCF₃ Br OCH₃ A-239 OC(═O)CH₃ Br OCH₃ A-240 OC(═O)CH₂CH₃ Br OCH₃ A-241 I I OCH₃ A-242 OH I OCH₃ A-243 SH I OCH₃ A-244 SCH₃ I OCH₃ A-245 NH₂ I OCH₃ A-246 OCH₃ I OCH₃ A-247 OCHF₂ I OCH₃ A-248 OCHFCl I OCH₃ A-249 OCF₃ I OCH₃ A-250 OC(═O)CH₃ I OCH₃ A-251 OC(═O)CH₂CH₃ I OCH₃ A-252 OH OH OCH₃ A-253 SH OH OCH₃ A-254 SCH₃ OH OCH₃ A-255 NH₂ OH OCH₃ A-256 OCH₃ OH OCH₃ A-257 OCHF₂ OH OCH₃ A-258 OCHFCl OH OCH₃ A-259 OCF₃ OH OCH₃ A-260 OC(═O)CH₃ OH OCH₃ A-261 OC(═O)CH₂CH₃ OH OCH₃ A-262 SH SH OCH₃ A-263 SCH₃ SH OCH₃ A-264 NH₂ SH OCH₃ A-265 OCH₃ SH OCH₃ A-266 OCHF₂ SH OCH₃ A-267 OCHFCl SH OCH₃ A-268 OCF₃ SH OCH₃ A-269 OC(═O)CH₃ SH OCH₃ A-270 OC(═O)CH₂CH₃ SH OCH₃ A-271 SCH₃ SCH₃ OCH₃ A-272 NH₂ SCH₃ OCH₃ A-273 OCH₃ SCH₃ OCH₃ A-274 OCHF₂ SCH₃ OCH₃ A-275 OCHFCl SCH₃ OCH₃ A-276 OCF₃ SCH₃ OCH₃ A-277 OC(═O)CH₃ SCH₃ OCH₃ A-278 OC(═O)CH₂CH₃ SCH₃ OCH₃ A-279 NH₂ NH₂ OCH₃ A-280 OCH₃ NH₂ OCH₃ A-281 OCHF₂ NH₂ OCH₃ A-282 OCHFCl NH₂ OCH₃ A-283 OCF₃ NH₂ OCH₃ A-284 OC(═O)CH₃ NH₂ OCH₃ A-285 OC(═O)CH₂CH₃ NH₂ OCH₃ A-286 OCH₃ OCH₃ OCH₃ A-287 OCHF₂ OCH₃ OCH₃ A-288 OCHFCl OCH₃ OCH₃ A-289 OCF₃ OCH₃ OCH₃ A-290 OC(═O)CH₃ OCH₃ OCH₃ A-291 OC(═O)CH₂CH₃ OCH₃ OCH₃ A-292 OCHF₂ OCHF₂ OCH₃ A-293 OCHFCl OCHF₂ OCH₃ A-294 OCF₃ OCHF₂ OCH₃ A-295 OC(═O)CH₃ OCHF₂ OCH₃ A-296 OC(═O)CH₂CH₃ OCHF₂ OCH₃ A-297 OCHFCl OCHFCl OCH₃ A-298 OCF₃ OCHFCl OCH₃ A-299 OC(═O)CH₃ OCHFCl OCH₃ A-300 OC(═O)CH₂CH₃ OCHFCl OCH₃ A-301 OCF₃ OCF₃ OCH₃ A-302 OC(═O)CH₃ OCF₃ OCH₃ A-303 OC(═O)CH₂CH₃ OCF₃ OCH₃ A-304 OC(═O)CH₃ OC(═O)CH₃ OCH₃ A-305 OC(═O)CH₂CH₃ OC(═O)CH₃ OCH₃ A-306 OC(═O)CH₂CH₃ OC(═O)CH₂CH₃ OCH₃ A-307 CH₃ CH₃ OCH₂CH₃ A-308 CH₂CH₃ CH₃ OCH₂CH₃ A-309 CF₃ CH₃ OCH₂CH₃ A-310 F CH₃ OCH₂CH₃ A-311 Cl CH₃ OCH₂CH₃ A-312 Br CH₃ OCH₂CH₃ A-313 I CH₃ OCH₂CH₃ A-314 OH CH₃ OCH₂CH₃ A-315 SH CH₃ OCH₂CH₃ A-316 SCH₃ CH₃ OCH₂CH₃ A-317 NH₂ CH₃ OCH₂CH₃ A-318 OCH₃ CH₃ OCH₂CH₃ A-319 OCHF₂ CH₃ OCH₂CH₃ A-320 OCHFCl CH₃ OCH₂CH₃ A-321 OCF₃ CH₃ OCH₂CH₃ A-322 OC(═O)CH₃ CH₃ OCH₂CH₃ A-323 OC(═O)CH₂CH₃ CH₃ OCH₂CH₃ A-324 CH₂CH₃ CH₂CH₃ OCH₂CH₃ A-325 CF₃ CH₂CH₃ OCH₂CH₃ A-326 F CH₂CH₃ OCH₂CH₃ A-327 Cl CH₂CH₃ OCH₂CH₃ A-328 Br CH₂CH₃ OCH₂CH₃ A-329 I CH₂CH₃ OCH₂CH₃ A-330 OH CH₂CH₃ OCH₂CH₃ A-331 SH CH₂CH₃ OCH₂CH₃ A-332 SCH₃ CH₂CH₃ OCH₂CH₃ A-333 NH₂ CH₂CH₃ OCH₂CH₃ A-334 OCH₃ CH₂CH₃ OCH₂CH₃ A-335 OCHF₂ CH₂CH₃ OCH₂CH₃ A-336 OCHFCl CH₂CH₃ OCH₂CH₃ A-337 OCF₃ CH₂CH₃ OCH₂CH₃ A-338 OC(═O)CH₃ CH₂CH₃ OCH₂CH₃ A-339 OC(═O)CH₂CH₃ CH₂CH₃ OCH₂CH₃ A-340 CF₃ CF₃ OCH₂CH₃ A-341 F CF₃ OCH₂CH₃ A-342 Cl CF₃ OCH₂CH₃ A-343 Br CF₃ OCH₂CH₃ A-344 I CF₃ OCH₂CH₃ A-345 OH CF₃ OCH₂CH₃ A-346 SH CF₃ OCH₂CH₃ A-347 SCH₃ CF₃ OCH₂CH₃ A-348 NH₂ CF₃ OCH₂CH₃ A-349 OCH₃ CF₃ OCH₂CH₃ A-350 OCHF₂ CF₃ OCH₂CH₃ A-351 OCHFCl CF₃ OCH₂CH₃ A-352 OCF₃ CF₃ OCH₂CH₃ A-353 OC(═O)CH₃ CF₃ OCH₂CH₃ A-354 OC(═O)CH₂CH₃ CF₃ OCH₂CH₃ A-355 F F OCH₂CH₃ A-356 Cl F OCH₂CH₃ A-357 Br F OCH₂CH₃ A-358 I F OCH₂CH₃ A-359 OH F OCH₂CH₃ A-360 SH F OCH₂CH₃ A-361 SCH₃ F OCH₂CH₃ A-362 NH₂ F OCH₂CH₃ A-363 OCH₃ F OCH₂CH₃ A-364 OCHF₂ F OCH₂CH₃ A-365 OCHFCl F OCH₂CH₃ A-366 OCF₃ F OCH₂CH₃ A-367 OC(═O)CH₃ F OCH₂CH₃ A-368 OC(═O)CH₂CH₃ F OCH₂CH₃ A-369 Cl Cl OCH₂CH₃ A-370 Br Cl OCH₂CH₃ A-37l I Cl OCH₂CH₃ A-372 OH Cl OCH₂CH₃ A-373 SH Cl OCH₂CH₃ A-374 SCH₃ Cl OCH₂CH₃ A-375 NH₂ Cl OCH₂CH₃ A-376 OCH₃ Cl OCH₂CH₃ A-377 OCHF₂ Cl OCH₂CH₃ A-378 OCHFCl Cl OCH₂CH₃ A-379 OCF₃ Cl OCH₂CH₃ A-380 OC(═O)CH₃ Cl OCH₂CH₃ A-381 OC(═O)CH₂CH₃ Cl OCH₂CH₃ A-382 Br Br OCH₂CH₃ A-383 I Br OCH₂CH₃ A-384 OH Br OCH₂CH₃ A-385 SH Br OCH₂CH₃ A-386 SCH₃ Br OCH₂CH₃ A-387 NH₂ Br OCH₂CH₃ A-388 OCH₃ Br OCH₂CH₃ A-389 OCHF₂ Br OCH₂CH₃ A-390 OCHFCl Br OCH₂CH₃ A-391 OCF₃ Br OCH₂CH₃ A-392 OC(═O)CH₃ Br OCH₂CH₃ A-393 OC(═O)CH₂CH₃ Br OCH₂CH₃ A-394 I I OCH₂CH₃ A-395 OH I OCH₂CH₃ A-396 SH I OCH₂CH₃ A-397 SCH₃ I OCH₂CH₃ A-398 NH₂ I OCH₂CH₃ A-399 OCH₃ I OCH₂CH₃ A-400 OCHF₂ I 0CH₂CH₃ A-401 OCHFCl I OCH₂CH₃ A-402 OCF₃ I OCH₂CH₃ A-403 OC(═O)CH₃ I OCH₂CH₃ A-404 OC(═O)CH₂CH₃ I OCH₂CH₃ A-405 OH OH OCH₂CH₃ A-406 SH OH OCH₂CH₃ A-407 SCH₃ OH OCH₂CH₃ A-408 NH₂ OH OCH₂CH₃ A-409 OCH₃ OH OCH₂CH₃ A-410 OCHF₂ OH OCH₂CH₃ A-411 OCHFCl OH OCH₂CH₃ A-412 OCF₃ OH OCH₂CH₃ A-413 OC(═O)CH₃ OH OCH₂CH₃ A-414 OC(═O)CH₂CH₃ OH OCH₂CH₃ A-415 SH SH OCH₂CH₃ A-416 SCH₃ SH OCH₂CH₃ A-417 NH₂ SH OCH₂CH₃ A-418 OCH₃ SH OCH₂CH₃ A-419 OCHF₂ SH OCH₂CH₃ A-420 OCHFCl SH OCH₂CH₃ A-421 OCF₃ SH OCH₂CH₃ A-422 OC(═O)CH₃ SH OCH₂CH₃ A-423 OC(═O)CH₂CH₃ SH OCH₂CH₃ A-424 SCH₃ SCH₃ OCH₂CH₃ A-425 NH₂ SCH₃ OCH₂CH₃ A-426 OCH₃ SCH₃ OCH₂CH₃ A-427 OCHF₂ SCH₃ OCH₂CH₃ A-428 OCHFCl SCH₃ OCH₂CH₃ A-429 OCF₃ SCH₃ OCH₂CH₃ A-430 OC(═O)CH₃ SCH₃ OCH₂CH₃ A-431 OC(═O)CH₂CH₃ SCH₃ OCH₂CH₃ A-432 NH₂ NH₂ OCH₂CH₃ A-433 OCH₃ NH₂ OCH₂CH₃ A-434 OCHF₂ NH₂ OCH₂CH₃ A-435 OCHFCl NH₂ OCH₂CH₃ A-436 OCF₃ NH₂ OCH₂CH₃ A-437 OC(═O)CH₃ NH₂ OCH₂CH₃ A-438 OC(═O)CH₂CH₃ NH₂ OCH₂CH₃ A-439 OCH₃ OCH₃ OCH₂CH₃ A-440 OCHF₂ OCH₃ OCH₂CH₃ A-441 OCHFCl OCH₃ OCH₂CH₃ A-442 OCF₃ OCH₃ OCH₂CH₃ A-443 OC(═O)CH₃ OCH₃ OCH₂CH₃ A-444 OC(═O)CH₂CH₃ OCH₃ OCH₂CH₃ A-445 OCHF₂ OCHF₂ OCH₂CH₃ A-446 OCHFCl OCHF₂ OCH₂CH₃ A-447 OCF₃ OCHF₂ OCH₂CH₃ A-448 OC(═O)CH₃ OCHF₂ OCH₂CH₃ A-449 OC(═O)CH₂CH₃ OCHF₂ OCH₂CH₃ A-450 OCHFCl OCHFCl OCH₂CH₃ A-451 OCF₃ OCHFCl OCH₂CH₃ A-452 OC(═O)CH₃ OCHFCl OCH₂CH₃ A-453 OC(═O)CH₂CH₃ OCHFCl OCH₂CH₃ A-454 OCF₃ OCF₃ OCH₂CH₃ A-455 OC(═O)CH₃ OCF₃ OCH₂CH₃ A-456 OC(═O)CH₂CH₃ OCF₃ OCH₂CH₃ A-457 OC(═O)CH₃ OC(═O)CH₃ OCH₂CH₃ A-458 OC(═O) CH₂CH₃ OC(═O)CH₃ OCH₂CH₃ A-459 OC(═O)CH₂CH₃ OC(═O)CH₂CH₃ OCH₂CH₃ A-460 CH₃ CH₃ OCH₂CH₂CH₃ A-461 CH₂CH₃ CH₃ OCH₂CH₂CH₃ A-462 CF₃ CH₃ OCH₂CH₂CH₃ A-463 F CH₃ OCH₂CH₂CH₃ A-464 Cl CH₃ OCH₂CH₂CH₃ A-465 Br CH₃ OCH₂CH₂CH₃ A-466 I CH₃ OCH₂CH₂CH₃ A-467 OH CH₃ OCH₂CH₂CH₃ A-468 SH CH₃ OCH₂CH₂CH₃ A-469 SCH₃ CH₃ OCH₂CH₂CH₃ A-470 NH₂ CH₃ OCH₂CH₂CH₃ A-471 OCH₃ CH₃ OCH₂CH₂CH₃ A-472 OCHF₂ CH₃ OCH₂CH₂CH₃ A-473 OCHFCl CH₃ OCH₂CH₂CH₃ A-474 OCF₃ CH₃ OCH₂CH₂CH₃ A-475 OC(═O)CH₃ CH₃ OCH₂CH₂CH₃ A-476 OC(═O)CH₂CH₃ CH₃ OCH₂CH₂CH₃ A-477 CH₂CH₃ CH₂CH₃ OCH₂CH₂CH₃ A-478 CF₃ CH₂CH₃ OCH₂CH₂CH₃ A-479 F CH₂CH₃ OCH₂CH₂CH₃ A-480 Cl CH₂CH₃ OCH₂CH₂CH₃ A-481 Br CH₂CH₃ OCH₂CH₂CH₃ A-482 I CH₂CH₃ OCH₂CH₂CH₃ A-483 OH CH₂CH₃ OCH₂CH₂CH₃ A-484 SH CH₂CH₃ OCH₂CH₂CH₃ A-485 SCH₃ CH₂CH₃ OCH₂CH₂CH₃ A-486 NH₂ CH₂CH₃ OCH₂CH₂CH₃ A-487 OCH₃ CH₂CH₃ OCH₂CH₂CH₃ A-488 OCHF₂ CH₂CH₃ OCH₂CH₂CH₃ A-489 OCHFCl CH₂CH₃ OCH₂CH₂CH₃ A-490 OCF₃ CH₂CH₃ OCH₂CH₂CH₃ A-491 OC(═O)CH₃ CH₂CH₃ OCH₂CH₂CH₃ A-492 OC(═O)CH₂CH₃ CH₂CH₃ OCH₂CH₂CH₃ A-493 CF₃ CF₃ OCH₂CH₂CH₃ A-494 F CF₃ OCH₂CH₂CH₃ A-495 Cl CF₃ OCH₂CH₂CH₃ A-496 Br CF₃ OCH₂CH₂CH₃ A-497 I CF₃ OCH₂CH₂CH₃ A-498 OH CF₃ OCH₂CH₂CH₃ A-499 SH CF₃ OCH₂CH₂CH₃ A-500 SCH₃ CF₃ OCH₂CH₂CH₃ A-501 NH₂ CF₃ OCH₂CH₂CH₃ A-502 OCH₃ CF₃ OCH₂CH₂CH₃ A-503 OCHF₂ CF₃ OCH₂CH₂CH₃ A-504 OCHFCl CF₃ OCH₂CH₂CH₃ A-505 OCF₃ CF₃ OCH₂CH₂CH₃ A-506 OC(═O)CH₃ CF₃ OCH₂CH₂CH₃ A-507 OC(═O)CH₂CH₃ CF₃ OCH₂CH₂CH₃ A-508 F F OCH₂CH₂CH₃ A-509 Cl F OCH₂CH₂CH₃ A-510 Br F OCH₂CH₂CH₃ A-511 I F OCH₂CH₂CH₃ A-512 OH F OCH₂CH₂CH₃ A-513 SH F OCH₂CH₂CH₃ A-514 SCH₃ F OCH₂CH₂CH₃ A-515 NH₂ F OCH₂CH₂CH₃ A-516 OCH₃ F OCH₂CH₂CH₃ A-517 OCHF₂ F OCH₂CH₂CH₃ A-518 OCHFCl F OCH₂CH₂CH₃ A-519 OCF₃ F OCH₂CH₂CH₃ A-520 OC(═O)CH₃ F OCH₂CH₂CH₃ A-521 OC(═O)CH₂CH₃ F OCH₂CH₂CH₃ A-522 Cl Cl OCH₂CH₂CH₃ A-523 Br Cl OCH₂CH₂CH₃ A-524 I Cl OCH₂CH₂CH₃ A-525 OH Cl OCH₂CH₂CH₃ A-526 SH Cl OCH₂CH₂CH₃ A-527 SCH₃ Cl OCH₂CH₂CH₃ A-528 NH₂ Cl OCH₂CH₂CH₃ A-529 OCH₃ Cl OCH₂CH₂CH₃ A-530 OCHF₂ Cl OCH₂CH₂CH₃ A-531 OCHFCl Cl OCH₂CH₂CH₃ A-532 OCF₃ Cl OCH₂CH₂CH₃ A-533 OC(═O)CH₃ Cl OCH₂CH₂CH₃ A-534 OC(═O)CH₂CH₃ Cl OCH₂CH₂CH₃ A-535 Br Br OCH₂CH₂CH₃ A-536 I Br OCH₂CH₂CH₃ A-537 OH Br OCH₂CH₂CH₃ A-538 SH Br OCH₂CH₂CH₃ A-539 SCH₃ Br OCH₂CH₂CH₃ A-540 NH₂ Br OCH₂CH₂CH₃ A-541 OCH₃ Br OCH₂CH₂CH₃ A-542 OCHF₂ Br OCH₂CH₂CH₃ A-543 OCHFCl Br OCH₂CH₂CH₃ A-544 OCF₃ Br OCH₂CH₂CH₃ A-545 OC(═O)CH₃ Br OCH₂CH₂CH₃ A-546 OC(═O)CH₂CH₃ Br OCH₂CH₂CH₃ A-547 I I OCH₂CH₂CH₃ A-548 OH I OCH₂CH₂CH₃ A-549 SH I OCH₂CH₂CH₃ A-550 SCH₃ I OCH₂CH₂CH₃ A-551 NH₂ I OCH₂CH₂CH₃ A-552 OCH₃ I OCH₂CH₂CH₃ A-553 OCHF₂ I OCH₂CH₂CH₃ A-554 OCHFCl I OCH₂CH₂CH₃ A-555 OCF₃ I OCH₂CH₂CH₃ A-556 OC(═O)CH₃ I OCH₂CH₂CH₃ A-557 OC(═O)CH₂CH₃ I OCH₂CH₂CH₃ A-558 OH OH OCH₂CH₂CH₂ A-559 SH OH OCH₂CH₂CH₃ A-560 SCH₃ OH OCH₂CH₂CH₃ A-561 NH₂ OH OCH₂CH₂CH₃ A-562 OCH₃ OH OCH₂CH₂CH₃ A-563 OCHF₂ OH OCH₂CH₂CH₃ A-564 OCHFCl OH OCH₂CH₂CH₃ A-565 OCF₃ OH OCH₂CH₂CH₃ A-566 OC(═O)CH₃ OH OCH₂CH₂CH₃ A-567 OC(═O)CH₂CH₃ OH OCH₂CH₂CH₃ A-568 SH SH OCH₂CH₂CH₃ A-569 SCH₃ SH OCH₂CH₂CH₃ A-570 NH₂ SH OCH₂CH₂CH₃ A-571 OCH₃ SH OCH₂CH₂CH₃ A-572 OCHF₂ SH OCH₂CH₂CH₃ A-573 OCHFCl SH OCH₂CH₂CH₃ A-574 OCF₃ SH OCH₂CH₂CH₃ A-575 OC(═O)CH₃ SH OCH₂CH₂CH₃ A-576 OC(═O)CH₂CH₃ SH OCH₂CH₂CH₃ A-577 SCH₃ SCH₃ OCH₂CH₂CH₃ A-578 NH₂ SCH₃ OCH₂CH₂CH₃ A-579 OCH₃ SCH₃ OCH₂CH₂CH₃ A-580 OCHF₂ SCH₃ OCH₂CH₂CH₃ A-581 OCHFCl SCH₃ OCH₂CH₂CH₃ A-582 OCF₃ SCH₃ OCH₂CH₂CH₃ A-583 OC(═O)CH₃ SCH₃ OCH₂CH₂CH₃ A-584 OC(═O)CH₂CH₃ SCH₃ OCH₂CH₂CH₃ A-585 NH₂ NH₂ OCH₂CH₂CH₃ A-586 OCH₃ NH₂ OCH₂CH₂CH₃ A-587 OCHF₂ NH₂ OCH₂CH₂CH₃ A-588 OCHFCl NH₂ OCH₂CH₂CH₃ A-589 OCF₃ NH₂ OCH₂CH₂CH₃ A-590 OC(═O)CH₃ NH₂ OCH₂CH₂CH₃ A-591 OC(═O)CH₂CH₃ NH₂ OCH₂CH₂CH₃ A-592 OCH₃ OCH₃ OCH₂CH₂CH₃ A-593 OCHF₂ OCH₃ OCH₂CH₂CH₃ A-594 OCHFCl OCH₃ OCH₂CH₂CH₃ A-595 OCF₃ OCH₃ OCH₂CH₂CH₃ A-596 OC(═O)CH₃ OCH₃ OCH₂CH₂CH₃ A-597 OC(═O)CH₂CH₃ OCH₃ OCH₂CH₂CH₃ A-598 OCHF₂ OCHF₂ OCH₂CH₂CH₃ A-599 OCHFCl OCHF₂ OCH₂CH₂CH₃ A-600 OCF₃ OCHF₂ OCH₂CH₂CH₃ A-601 OC(═O)CH₃ OCHF₂ OCH₂CH₂CH₃ A-602 OC(═O)CH₂CH₃ OCHF₂ OCH₂CH₂CH₃ A-603 OCHFCl OCHFCl OCH₂CH₂CH₃ A-604 OCF₃ OCHFCl OCH₂CH₂CH₃ A-605 OC(═O)CH₃ OCHFCl OCH₂CH₂CH₃ A-606 OC(═O)CH₂CH₃ OCHFCl OCH₂CH₂CH₃ A-607 OCF₃ OCF₃ OCH₂CH₂CH₃ A-608 OC(═O)CH₃ OCF₃ OCH₂CH₂CH₃ A-609 OC(═O)CH₂CH₃ OCF₃ OCH₂CH₂CH₃ A-610 OC(═O)CH₃ OC(═O)CH₃ OCH₂CH₂CH₃ A-611 OC(═O)CH₂CH₃ OC(═O)CH₃ OCH₂CH₂CH₃ A-612 OC(═O)CH₂CH₃ OC(═O)CH₂CH₃ OCH₂CH₂CH₃ A-613 CH₃ CH₃ OCH(CH₃)₂ A-614 CH₂CH₃ CH₃ OCH(CH₃)₂ A-615 CF₃ CH₃ OCH(CH₃)₂ A-616 F CH₃ OCH(CH₃)₂ A-617 Cl CH₃ OCH(CH₃)₂ A-618 Br CH₃ OCH(CH₃)₂ A-619 I CH₃ OCH(CH₃)₂ A-620 OH CH₃ OCH(CH₃)₂ A-621 SH CH₃ OCH(CH₃)₂ A-622 SCH₃ CH₃ OCH(CH₃)₂ A-623 NH₂ CH₃ OCH(CH₃)₂ A-624 OCH₃ CH₃ OCH(CH₃)₂ A-625 OCHF₂ CH₃ OCH(CH₃)₂ A-626 OCHFCl CH₃ OCH(CH₃)₂ A-627 OCF₃ CH₃ OCH(CH₃)₂ A-628 OC(═O)CH₃ CH₃ OCH(CH₃)₂ A-629 OC(═O)CH₂CH₃ CH₃ OCH(CH₃)₂ A-630 CH₂CH₃ CH₂CH₃ OCH(CH₃₎ ₂ A-631 CF₃ CH₂CH₃ OCH(CH₃)₂ A-632 F CH₂CH₃ OCH(CH₃)₂ A-633 Cl CH₂CH₃ OCH(CH₃)₂ A-634 Br CH₂CH₃ OCH(CH₃)₂ A-635 I CH₂CH₃ OCH(CH₃)₂ A-636 OH CH₂CH₃ OCH(CH₃)₂ A-637 SH CH₂CH₃ OCH(CH₃)₂ A-638 SCH₃ CH₂CH₃ OCH(CH₃)₂ A-639 NH₂ CH₂CH₃ OCH(CH₃)₂ A-640 OCH₃ CH₂CH₃ OCH(CH₃)₂ A-641 OCHF₂ CH₂CH₃ OCH(CH₃)₂ A-642 OCHFCl CH₂CH₃ OCH(CH₃)₂ A-643 OCF₃ CH₂CH₃ OCH(CH₃)₂ A-644 OC(═O)CH₃ CH₂CH₃ OCH(CH₃)₂ A-645 OC(═O)CH₂CH₃ CH₂CH₃ OCH(CH₃)₂ A-646 CF₃ CF₃ OCH(CH₃)₂ A-647 F CF₃ OCH(CH₃)₂ A-648 Cl CF₃ OCH(CH₃)₂ A-649 Br CF₃ OCH(CH₃)₂ A-650 I CF₃ OCH(CH₃)₂ A-651 OH CF₃ OCH(CH₃)₂ A-652 SH CF₃ OCH(CH₃)₂ A-653 SCH₃ CF₃ OCH(CH₃)₂ A-654 NH₂ CF₃ OCH(CH₃)₂ A-655 OCH₃ CF₃ OCH(CH₃)₂ A-656 OCHF₂ CF₃ OCH(CH₃)₂ A-657 OCHFCl CF₃ OCH(CH₃)₂ A-658 OCF₃ CF₃ OCH(CH₃)₂ A-659 OC(═O)CH₃ CF₃ OCH(CH₃)₂ A-660 OC(═O)CH₂CH₃ CF₃ OCH(CH₃)₂ A-661 F F OCH(CH₃)₂ A-662 Cl F OCH(CH₃)₂ A-663 Br F OCH(CH₃)₂ A-664 I F OCH(CH₃)₂ A-665 OH F OCH(CH₃)₂ A-666 SH F OCH(CH₃)₂ A-667 SCH₃ F OCH(CH₃)₂ A-668 NH₂ F OCH(CH₃)₂ A-659 OCH₃ F OCH(CH₃)₂ A-670 OCHF₂ F OCH(CH₃)₂ A-671 OCHFCl F OCH(CH₃)₂ A-672 OCF₃ F OCH(CH₃)₂ A-673 OC(═O)CH₃ F OCH(CH₃)₂ A-674 OC(═O)CH₂CH₃ F OCH(CH₃)₂ A-675 Cl Cl OCH(CH₃)₂ A-676 Br Cl OCH(CH₃)₂ A-677 I Cl OCH(CH₃)₂ A-678 OH Cl OCH(CH₃)₂ A-679 SH Cl OCH(CH₃)₂ A-680 SCH₃ Cl OCH(CH₃)₂ A-681 NH₂ Cl OCH(CH₃)₂ A-682 OCH₃ Cl OCH(CH₃)₂ A-683 OCHF₂ Cl OCH(CH₃)₂ A-684 OCHFCl Cl OCH(CH₃)₂ A-685 OCF₃ Cl OCH(CH₃)₂ A-686 OC(═O)CH₃ Cl OCH(CH₃)₂ A-687 OC(═O)CH₂CH₃ Cl OCH(CH₃)₂ A-688 Br Br OCH(CH₃)₂ A-689 I Br OCH(CH₃)₂ A-690 OH Br OCH(CH₃)₂ A-69l SH Br OCH(CH₃)₂ A-692 SCH₃ Br OCH(CH₃)₂ A-693 NH₂ Br OCH(CH₃)₂ A-694 OCH₃ Br OCH(CH₃)₂ A-695 OCHF₂ Br OCH(CH₃)₂ A-696 OCHFCl Br OCH(CH₃)₂ A-697 OCF₃ Br OCH(CH₃)₂ A-698 OC(═O)CH₃ Br OCH(CH₃)₂ A-699 OC(═O)CH₂CH₃ Br OCH(CH₃)₂ A-700 I I OCH(CH₃)₂ A-701 OH I OCH(CH₃)₂ A-702 SH I OCH(CH₃)₂ A-703 SCH₃ I OCH(CH₃)₂ A-704 NH₂ I OCH(CH₃)₂ A-705 OCH₃ I OCH(CH₃)₂ A-706 OCHF₂ I OCH(CH₃)₂ A-707 OCHFCl I OCH(CH₃)₂ A-708 OCF₃ I OCH(CH₃)₂ A-709 OC(═O)CH₃ I OCH(CH₃)₂ A-710 OC(═O)CH₂CH₃ I OCH(CH₃)₂ A-711 OH OH OCH(CH₃)₂ A-712 SH OH OCH(CH₃)₂ A-713 SCH₃ OH OCH(CH₃)₂ A-714 NH₂ OH OCH(CH₃)₂ A-715 OCH₃ OH OCH(CH₃)₂ A-716 OCHF₂ OH OCH(CH₃)₂ A-717 OCHFCl OH OCH(CH₃)₂ A-718 OCF₃ OH OCH(CH₃)₂ A-719 OC(═O)CH₃ OH OCH(CH₃)₂ A-720 OC(═O)CH₂CH₃ OH OCH(CH₃)₂ A-721 SH SH OCH(CH₃)₂ A-722 SCH₃ SH OCH(CH₃)₂ A-723 NH₂ SH OCH(CH₃)₂ A-724 OCH₃ SH OCH(CH₃)₂ A-725 OCHF₂ SH OCH(CH₃)₂ A-726 OCHFCl SH OCH(CH₃)₂ A-727 OCF₃ SH OCH(CH₃)₂ A-728 OC(═O)CH₃ SH OCH(CH₃)₂ A-729 OC(═O)CH₂CH₃ SH OCH(CH₃)₂ A-730 SCH₃ SCH₃ OCH(CH₃)₂ A-731 NH₂ SCH₃ OCH(CH₃)₂ A-732 OCH₃ SCH₃ OCH(CH₃)₂ A-733 OCHF₂ SCH₃ OCH(CH₃)₂ A-734 OCHFCl SCH₃ OCH(CH₃)₂ A-735 OCF₃ SCH₃ OCH(CH₃)₂ A-736 OC(═O)CH₃ SCH₃ OCH(CH₃)₂ A-737 OC(═O)CH₂CH₃ SCH₃ OCH(CH₃)₂ A-738 NH₂ NH₂ OCH(CH₃)₂ A-739 OCH₃ NH₂ OCH(CH₃)₂ A-740 OCHF₂ NH₂ OCH(CH₃)₂ A-741 OCHFCl NH₂ OCH(CH₃)₂ A-742 OCF₃ NH₂ OCH(CH₃)₂ A-743 OC(═O)CH₃ NH₂ OCH(CH₃)₂ A-744 OC(═O)CH₂CH₃ NH₂ OCH(CH₃)₂ A-745 OCH₃ OCH₃ OCH(CH₃)₂ A-746 OCHF₂ OCH₃ OCH(CH₃)₂ A-747 OCHFCl OCH₃ OCH(CH₃)₂ A-748 OCF₃ OCH₃ OCH(CH₃)₂ A-749 OC(═O)CH₃ OCH₃ OCH(CH₃)₂ A-750 OC(═O)CH₂CH₃ OCH₃ OCH(CH₃)₂ A-751 OCHF₂ OCHF₂ OCH(CH₃)₂ A-752 OCHFCl OCHF₂ OCH(CH₃)₂ A-753 OCF₃ OCHF₂ OCH(CH₃)₂ A-754 OC(═O)CH₃ OCHF₂ OCH(CH₃)₂ A-755 OC(═O)CH₂CH₃ OCHF₂ OCH(CH₃)₂ A-756 OCHFCl OCHFCl OCH(CH₃)₂ A-757 OCF₃ OCHFCl OCH(CH₃)₂ A-758 OC(═O)CH₃ OCHFCl OCH(CH₃)₂ A-759 OC(═O)CH₂CH₃ OCHFCl OCH(CH₃)₂ A-760 OCF₃ OCF₃ OCH(CH₃)₂ A-761 OC(═O)CH₃ OCF₃ OCH(CH₃)₂ A-762 OC(═O)CH₂CH₃ OCF₃ OCH(CH₃)₂ A-763 OC(═O)CH₃ OC(═O)CH₃ OCH(CH₃)₂ A-764 OC(═O)CH₂CH₃ OC(═O)CH₃ OCH(CH₃)₂ A-765 OC(═O)CH₂CH₃ OC(═O)CH₂CH₃ OCH(CH₃)₂ A-766 CH₃ CH₃ OCH₂CH₂CH₂CH₃ A-767 CH₂CH₃ CH₃ OCH₂CH₂CH₂CH₃ A-768 CF₃ CH₃ OCH₂CH₂CH₂CH₃ A-769 F CH₃ OCH₂CH₂CH₂CH₃ A-770 Cl CH₃ OCH₂CH₂CH₂CH₃ A-771 Br CH₃ OCH₂CH₂CH₂CH₃ A-772 I CH₃ OCH₂CH₂CH₂CH₃ A-773 OH CH₃ OCH₂CH₂CH₂CH₃ A-774 SH CH₃ OCH₂CH₂CH₂CH₃ A-775 SCH₃ CH₃ OCH₂CH₂CH₂CH₃ A-776 NH₂ CH₃ OCH₂CH₂CH₂CH₃ A-777 OCH₃ CH₃ OCH₂CH₂CH₂CH₃ A-778 OCHF₂ CH₃ OCH₂CH₂CH₂CH₃ A-779 OCHFCl CH₃ OCH₂CH₂CH₂CH₃ A-780 OCF₃ CH₃ OCH₂CH₂CH₂CH₃ A-781 OC(═O)CH₃ CH₃ OCH₂CH₂CH₂CH₃ A-782 OC(═O)CH₂CH₃ CH₃ OCH₂CH₂CH₂CH₃ A-783 CH₂CH₃ CH₂CH₃ OCH₂CH₂CH₂CH₃ A-784 CF₃ CH₂CH₃ OCH₂CH₂CH₂CH₃ A-785 F CH₂CH₃ OCH₂CH₂CH₂CH₃ A-786 Cl CH₂CH₃ OCH₂CH₂CH₂CH₃ A-787 Br CH₂CH₃ OCH₂CH₂CH₂CH₃ A-788 I CH₂CH₃ OCH₂CH₂CH₂CH₃ A-789 OH CH₂CH₃ OCH₂CH₂CH₂CH₃ A-790 SH CH₂CH₃ OCH₂CH₂CH₂CH₃ A-791 8CH₃ CH₂CH₃ OCH₂CH₂CH₂CH₃ A-792 NH₂ CH₂CH₃ OCH₂CH₂CH₂CH₃ A-793 OCH₃ CH₂CH₃ OCH₂CH₂CH₂CH₃ A-794 OCHF₂ CH₂CH₃ OCH₂CH₂CH₂CH₃ A-795 OCHFCl CH₂CH₃ OCH₂CH₂CH₂CH₃ A-796 OCF₃ CH₂CH₃ OCH₂CH₂CH₂CH₃ A-797 OC(═O)CH₃ CH₂CH₃ OCH₂CH₂CH₂CH₃ A-798 OC(═O)CH₂CH₃ CH₂CH₃ OCH₂CH₂CH₂CH₃ A-799 CF₃ CF₃ OCH₂CH₂CH₂CH₃ A-800 F CF₃ OCH₂CH₂CH₂CH₃ A-801 Cl CF₃ OCH₂CH₂CH₂CH₃ A-802 Br CF₃ OCH₂CH₂CH₂CH₃ A-803 I CF₃ OCH₂CH₂CH₂CH₃ A-804 OH CF₃ OCH₂CH₂CH₂CH₃ A-805 SH CF₃ OCH₂CH₂CH₂CH₃ A-806 SCH₃ CF₃ OCH₂CH₂CH₂CH₃ A-807 NH₂ CF₃ OCH₂CH₂CH₂CH₃ A-808 OCH₃ CF₃ OCH₂CH₂CH₂CH₃ A-809 OCHF₂ CF₃ OCH₂CH₂CH₂CH₃ A-810 OCHFCl CF₃ OCH₂CH₂CH₂CH₃ A-811 OCF₃ CF₃ OCH₂CH₂CH₂CH₃ A-812 OC(═O)CH₃ CF₃ OCH₂CH₂CH₂CH₃ A-813 OC(═O)CH₂CH₃ CF₃ OCH₂CH₂CH₂CH₃ A-814 F F OCH₂CH₂CH₂CH₃ A-815 Cl F OCH₂CH₂CH₂CH₃ A-816 Br F OCH₂CH₂CH₂CH₃ A-817 I F OCH₂CH₂CH₂CH₃ A-818 OH F OCH₂CH₂CH₂CH₃ A-819 SH F OCH₂CH₂CH₂CH₃ A-820 SCH₃ F OCH₂CH₂CH₂CH₃ A-821 NH₂ F OCH₂CH₂CH₂CH₃ A-822 OCH₃ F OCH₂CH₂CH₂CH₃ A-823 OCHF₂ F OCH₂CH₂CH₂CH₃ A-824 OCHFCl F OCH₂CH₂CH₂CH₃ A-825 OCF₃ F OCH₂CH₂CH₂CH₃ A-826 OC(═O)CH₃ F OCH₂CH₂CH₂CH₃ A-827 OC(═O)CH₂CH₃ F OCH₂CH₂CH₂CH₃ A-828 Cl Cl OCH₂CH₂CH₂CH₃ A-829 Br Cl OCH₂CH₂CH₂CH₃ A-830 I Cl OCH₂CH₂CH₂CH₃ A-831 OH Cl OCH₂CH₂CH₂CH₃ A-832 SH Cl OCH₂CH₂CH₂CH₃ A-833 SCH₃ Cl OCH₂CH₂CH₂CH₃ A-834 NH₂ Cl OCH₂CH₂CH₂CH₃ A-835 OCH₃ Cl OCH₂CH₂CH₂CH₃ A-836 OCHF₂ Cl OCH₂CH₂CH₂CH₃ A-837 OCHFCl Cl OCH₂CH₂CH₂CH₃ A-838 OCF₃ Cl OCH₂CH₂CH₂CH₃ A-839 OC(═O)CH₃ Cl OCH₂CH₂CH₂CH₃ A-840 OC(═O)CH₂CH₃ Cl OCH₂CH₂CH₂CH₃ A-841 Br Br OCH₂CH₂CH₂CH₃ A-842 I Br OCH₂CH₂CH₂CH₃ A-843 OH Br OCH₂CH₂CH₂CH₃ A-844 SH Br OCH₂CH₂CH₂CH₃ A-845 SCH₃ Br OCH₂CH₂CH₂CH₃ A-846 NH₂ Br OCH₂CH₂CH₂CH₃ A-847 OCH₃ Br OCH₂CH₂CH₂CH₃ A-848 OCHF₂ Br OCH₂CH₂CH₂CH₃ A-849 OCHFCl Br OCH₂CH₂CH₂CH₃ A-850 OCF₃ Br OCH₂CH₂CH₂CH₃ A-851 OC(═O)CH₃ Br OCH₂CH₂CH₂CH₃ A-852 OC(═O)CH₂CH₃ Br OCH₂CH₂CH₂CH₃ A-853 I I OCH₂CH₂CH₂CH₃ A-854 OH I OCH₂CH₂CH₂CH₃ A-855 SH I OCH₂CH₂CH₂CH₃ A-856 SCH₃ I OCH₂CH₂CH₂CH₃ A-857 NH₂ I OCH₂CH₂CH₂CH₃ A-858 OCH₃ I OCH₂CH₂CH₂CH₃ A-859 OCHF₂ I OCH₂CH₂CH₂CH₃ A-860 OCHFCl I OCH₂CH₂CH₂CH₃ A-861 OCF₃ I OCH₂CH₂CH₂CH₃ A-862 OC(═O)CH₃ I OCH₂CH₂CH₂CH₃ A-863 OC(═O)CH₂CH₃ I OCH₂CH₂CH₂CH₃ A-864 OH OH OCH₂CH₂CH₂CH₃ A-865 SH OH OCH₂CH₂CH₂CH₃ A-866 SCH₃ OH OCH₂CH₂CH₂CH₃ A-867 NH₂ OH OCH₂CH₂CH₂CH₃ A-868 OCH₃ OH OCH₂CH₂CH₂CH₃ A-869 OCHF₂ OH OCH₂CH₂CH₂CH₃ A-870 OCHFCl OH OCH₂CH₂CH₂CH₃ A-871 OCF₃ OH OCH₂CH₂CH₂CH₃ A-872 OC(═O)CH₃ OH OCH₂CH₂CH₂CH₃ A-873 OC(═O)CH₂CH₃ OH OCH₂CH₂CH₂CH₃ A-874 SH SH OCH₂CH₂CH₂CH₃ A-875 SCH₃ SH OCH₂CH₂CH₂CH₃ A-876 NH₂ SH OCH₂CH₂CH₂CH₃ A-877 OCH₃ SH OCH₂CH₂CH₂CH₃ A-878 OCHF₂ SH OCH₂CH₂CH₂CH₃ A-879 OCHFCl SH OCH₂CH₂CH₂CH₃ A-880 OCF₃ SH OCH₂CH₂CH₂CH₃ A-881 OC(═O)CH₃ SH OCH₂CH₂CH₂CH₃ A-882 OC(═O)CH₂CH₃ SH OCH₂CH₂CH₂CH₃ A-883 SCH₃ SCH₃ OCH₂CH₂CH₂CH₃ A-884 NH₂ SCH₃ OCH₂CH₂CH₂CH₃ A-885 OCH₃ SCH₃ OCH₂CH₂CH₂CH₃ A-886 OCHF₂ SCH₃ OCH₂CH₂CH₂CH₃ A-887 OCHFCl SCH₃ OCH₂CH₂CH₂CH₃ A-888 OCF₃ SCH₃ OCH₂CH₂CH₂CH₃ A-889 OC(═O)CH₃ SCH₃ OCH₂CH₂CH₂CH₃ A-890 OC(═O)CH₂CH₃ SCH₃ OCH₂CH₂CH₂CH₃ A-891 NH₂ NH₂ OCH₂CH₂CH₂CH₃ A-892 OCH₃ NH₂ OCH₂CH₂CH₂CH₃ A-893 OCHF₂ NH₂ OCH₂CH₂CH₂CH₃ A-894 OCHFCl NH₂ OCH₂CH₂CH₂CH₃ A-895 OCF₃ NH₂ OCH₂CH₂CH₂CH₃ A-896 OC(═O)CH₃ NH₂ OCH₂CH₂CH₂CH₃ A-897 OC(═O)CH₂CH₃ NH₂ OCH₂CH₂CH₂CH₃ A-898 OCH₃ OCH₃ OCH₂CH₂CH₂CH₃ A-899 OCHF₂ OCH₃ OCH₂CH₂CH₂CH₃ A-900 OCHFCl OCH₃ OCH₂CH₂CH₂CH₃ A-901 OCF₃ OCH₃ OCH₂CH₂CH₂CH₃ A-902 OC(═O)CH₃ OCH₃ OCH₂CH₂CH₂CH₃ A-903 OC(═O)CH₂CH₃ OCH₃ OCH₂CH₂CH₂CH₃ A-904 OCHF₂ OCHF₂ OCH₂CH₂CH₂CH₃ A-905 OCHFCl OCHF₂ OCH₂CH₂CH₂CH₃ A-906 OCF₃ OCHF₂ OCH₂CH₂CH₂CH₃ A-907 OC(═O)CH₃ OCHF₂ OCH₂CH₂CH₂CH₃ A-908 OC(═O)CH₂CH₃ OCHF₂ OCH₂CH₂CH₂CH₃ A-909 OCHFCl OCHFCl OCH₂CH₂CH₂CH₃ A-910 OCF₃ OCHFCl OCH₂CH₂CH₂CH₃ A-911 OC(═O)CH₃ OCHFCl OCH₂CH₂CH₂CH₃ A-912 OC(═O)CH₂CH₃ OCHFCl OCH₂CH₂CH₂CH₃ A-913 OCF₃ OCF₃ OCH₂CH₂CH₂CH₃ A-914 OC(═O)CH₃ OCF₃ OCH₂CH₂CH₂CH₃ A-915 OC(═O)CH₂CH₃ OCF₃ OCH₂CH₂CH₂CH₃ A-916 OC(═O)CH₃ OC(═O)CH₃ OCH₂CH₂CH₂CH₃ A-917 OC(═O)CH₂CH₃ OC(═O)CH₃ OCH₂CH₂CH₂CH₃ A-918 OC(═O)CH₂CH₃ OC(═O)CH₂CH₃ OCH₂CH₂CH₂CH₃

[0351] The compounds of the formula I can be obtained by different routes. Compounds of the formula I in which X is oxygen are obtained, for example, by reacting aldehydes of the formula II,

[0352] where the variables R¹, R², R³ and n are as defined for formula I and may be protected by a protective group Q which is removed after the reaction, with halobenzene derivatives of the formula III,

[0353] where the variables R⁴, R⁵ and R⁶ are as defined for formula I and A is halogen, and A is converted, in an intermediate step, into a group B, where B is a suitable metal or a suitable halometal group.

[0354] Suitable groups A are fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.

[0355] Suitable groups B are, for example, Li, Na, MgY (Y=halogen, in particular Br), Sn(R′)₂ (R′=CH₃, CH₂CH₃), ZnR′, Cu(CN)ZnI [cf. J. March, Advanced Organic Chemistry, J. Wiley & Sons, New York, 1992, pp. 920-929 and the literature cited therein].

[0356] Preferred groups B are Na and MgY.

[0357] The reaction is carried out by converting the halogen group A into the group B in a manner known per se, followed by in situ reaction of the resulting benzene derivatives with aldehydes of the formula II [cf. J. March, Advanced Organic Chemistry, J. Wiley & Sons, New York, 1992, pp. 920-929 and the literature cited therein].

[0358] If B is Li, Na or MgY, the reaction is carried out, for example, at temperatures of from −20° C. to 150° C., preferably from 20° C. to 100° C., in an inert organic solvent, using at least equimolar amounts of Li, Na or Mg, based on the halobenzene III, and, if B is Li or Na, if appropriate under reaction-accelerating conditions, such as the addition of dibromoethane or iodine, or the use of ultrasound [cf. J. March, Advanced Organic Chemistry, J. Wiley & Sons, New York, 1992, pp. 920-929 and the literature cited therein].

[0359] The protective group Q is introduced into the aldehydes of the formula II by methods known from the literature [cf. T. W. Greene, Protective Groups in Organic Chemistry, J. Wiley & Sons, 1991, pp. 10-142].

[0360] Suitable protective groups for R¹, R², R³=hydroxyl, mercapto or amino are, for example, groups that can be removed under Lewis-acidic conditions, such as alkyl, in particular methyl.

[0361] In a preferred embodiment of the reaction, the variables R¹, R² and R³ are inert under the reaction conditions.

[0362] For preparing compounds I in which R¹ and R³ contain carbonyl functionalities, the process described below, which uses the corresponding benzophenones IV as starting materials, is preferred.

[0363] Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitrites, such as acetonitrile and propionitrile, preferably ethers, very particularly preferably diethyl ether and tetrahydrofuran.

[0364] It is also possible to use mixtures of the solvents mentioned.

[0365] The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of compounds of the formula III, based on compounds of the formula II.

[0366] The reaction mixtures are worked up in a customary manner, for example by mixing with water, phase separation and, if required, chromatographic purification of the crude products. Some intermediates and end products are obtained in the form of colorless or slightly brownish, viscous oils, which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.

[0367] The starting materials of the formula II required for preparing the compounds I can be prepared, for example, by reducing the corresponding benzoic acids or benzoic esters with diisobutylaluminum hydride, described, for example, in EP-A 727 141, or they can be prepared in the manner known per se [cf. J. March, Advanced Organic Chemistry, J. Wiley & Sons, New York, 1992, pp. 501-521, pp 641-758, pp. 982-1161.].

[0368] The starting materials of the formula III required for preparing the compounds I can be prepared by methods known from the literature from gallic acid or its derivatives, or in a manner known per se [cf. J. March, Advanced Organic Chemistry, J. Wiley & Sons, New York, 1992, pp. 501-521, pp. 641-758, pp. 982-1161.]

[0369] Compounds of the formula I in which X is oxygen can also be prepared by reduction of the analogous benzophenone derivatives of the formula IV,

[0370] where the variables are as defined for formula I or denote a group which, after the reaction, can be converted into these radicals, using hydrides or by catalytic reduction with H₂.

[0371] Suitable hydrides are, preferably, borohydrides and aluminum hydrides, such as NaBH₄ or LiAlH₄ [cf. M. Hudlicky, Reductions in Organic Chemistry, ACS Monograph 188, American Chemical Society, Washington D.C., 1996, p. 152 ff.; Tetrahedron Lett. 28 (4), pp. 4725-4728 (1987)], or elemental aluminum in ammonia [cf. Chem. Soc. Jpn. 63(1), pp. 290-292 (1990)].

[0372] The reaction is usually carried out at temperatures of from −78° C. to 120° C., preferably from −78° C. to 0° C., in an inert organic solvent.

[0373] Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, preferably ethers, articularly preferably tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.

[0374] The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of reducing agent, based on compounds of the formula IV.

[0375] The reaction mixtures are worked up in a customary manner, for example by mixing with water, phase separation and, if required, chromatographic purification of the crude products. Some intermediates and end products are obtained in the form of colorless or slightly brownish, viscous oils, which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.

[0376] The reduction can also be carried out in the manner known per se using H₂ and catalysts based on transition metals. Suitable transition metals are palladium, platinum, rhodium and ruthenium.

[0377] This reaction is usually carried out at temperatures of from 0° C. to 150° C., preferably from 0° C. to 50° C., in an inert organic solvent [cf. Organotransition Metal Chemistry, Academic Press, New York, 1974, pp. 65-70 and the literature cited therein; JP-A 10273455].

[0378] Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, particularly preferably methanol, ethanol or isopropanol. It is also possible to use mixtures of the solvents mentioned.

[0379] In a preferred embodiment of the reduction with H₂, chiral catalysts are employed, so that it is possible to obtain the (R) or (S) isomer of the benzhydryl alcohol I in a selective manner [cf. Org. Lett. 2(5), pp. 659-662, (2000)].

[0380] If the variables R¹, R² or R³ are groups which can be reduced under the reaction conditions, such as nitro or formyl, it may be necessary to re-establish these groups after the reaction by selective oxidation. It may also be advantageous to introduce such reducible groups only after the reduction of the benzophenones IV has taken place, by oxidizing appropriate groups (for example introducing a nitro group by oxidation of an amino group or introducing a formyl group by oxidation of a hydroxyl group).

[0381] Compounds I in which R¹ is formyl can be obtained, for example, by selective oxidation of corresponding compounds in which R¹ is hydroxymethyl, which may be formed in the reduction according to the invention from a formyl group [cf. M. Hudlicky, Oxidations in Organic Chemistry, ACS Monograph 186, American Chemical Society, Washington D.C., 1990, pp. 114-127].

[0382] It may also be advantageous to obtain compounds of the formula I in which R¹ is hydroxyl by reducing compounds of the formula IV in which R¹ is alkylcarbonyloxy. Here, R¹ and the keto group that bridges the phenyl groups are reduced simultaneously.

[0383] For compounds I in which the variables R¹, R² , R³ or R⁴ are alkenyl or alkynyl, the process described above, which uses halobenzene derivatives III and aldehydes II as starting materials, is preferred.

[0384] The reaction mixtures are worked up in a customary manner, for example by mixing with water, phase separation and, if required, chromatographic purification of the crude products. Some intermediates and end products are obtained in the form of colorless or slightly brownish, viscous oils, which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.

[0385] The starting materials of the formula IV required for preparing the compounds I are known from the literature (for example from EP-A 727 141), or they can be prepared in accordance with the literature cited.

[0386] If individual compounds I are not accessible by the routes described above, they can be prepared by derivatization of other compounds I.

[0387] The benzhydryl thiols Ib can be obtained from the corresponding alcohols Ia under conditions known from the literature. The reaction is usually carried out at temperatures of from 0° C. to 180° C., preferably from 20° C. to 140° C., in an inert organic solvent [cf. Liebigs Ann. Chem., p. 177 (1989)].

[0388] Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, and dimethylene glycol, particularly preferably toluene and dimethylene glycol.

[0389] It is also possible to use mixtures of the solvents mentioned.

[0390] Suitable sulfurizing agents are, for example, phosphorus pentasulfide or Lawesson's reagent.

[0391] The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of sulfurizing agent, based on Ia.

[0392] Benzhydryl thiols Ib can also be obtained by reducing the corresponding thioketones V, which can be prepared from the benzophenones IV.

[0393] The reduction to give the benzhydryl thiols Ib can be carried out using, for example, borohydrides or aluminum hydrides [cf. Synth. Commun. 23 (9), pp. 1267-1271 (1993); Tetrahedron: Asymmetry 7(12), pp. 3553-3558 (1996); Can. J. Chem. 48, p. 3593, (1970)], or using elemental ytterbium in tetrahydrofuran [cf. Chem. Lett. 3, p. 611 (1994)].

[0394] The conversion of the benzophenones IV into the thioketones V is carried out analogously to the reaction of the benzhydryl alcohols Ia described above.

[0395] The compounds I are suitable as fungicides. They have excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them act systemically and can be employed in crop protection as foliar- and soil-acting fungicides.

[0396] They are especially important for controlling a large number of fungi in a variety of crop plants such as wheat, rye, barley, oats, rice, maize, grass, bananas, cotton, soya, coffee, sugar cane, grape vines, fruit species, ornamentals and vegetable species such as cucumbers, beans, tomatoes, potatoes and cucurbits, and also in the seeds of these plants.

[0397] Specifically, they are suitable for controlling the following plant diseases:

[0398] Alternaria species in vegetables and fruit,

[0399] Botrytis cinerea (gray mold) in strawberries, vegetables, ornamentals and grape vines,

[0400] Cercospora arachidicola in groundnuts,

[0401] Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

[0402] Erysiphe graminis (powdery mildew) in cereals,

[0403] Fusarium and Verticillium species in a variety of plants,

[0404] Helminthosporium species in cereals,

[0405] Mycosphaerella species in bananas and groundnuts,

[0406] Phytophthora infestans in potatoes and tomatoes,

[0407] Plasmopara viticola in grape vines,

[0408] Podosphaera leucotricha in apples,

[0409] Pseudocercosporella herpotrichoides in wheat and barley,

[0410] Pseudoperonospora species in hops and cucumbers,

[0411] Puccinia species in cereals,

[0412] Pyricularia oryzae in rice,

[0413] Rhizoctonia species in cotton, rice and lawns,

[0414] Septoria nodorum in wheat,

[0415] Uncinula necator in grape vines,

[0416] Ustilago species in cereals and sugar cane, and

[0417] Venturia species (scab) in apples and pears.

[0418] The compounds I are also suitable for controlling harmful fungi such as Paecilomyces variotii in the protection of materials (for example wood, paper, paint dispersions, fibers or tissues) and in the protection of stored products.

[0419] The compounds I are employed by treating the fungi or the plants, seeds, materials to be protected against fungal attack or the soil with a fungicidally effective amount of the active compounds. The application may be carried out before or after the infection of the materials, plants or seeds by the fungi.

[0420] The fungicidal compositions generally comprise from 0.1 to 95, preferably from 0.5 to 90, % by weight of active compound.

[0421] For use in crop protection, the application rates are, depending on the kind of effect desired, from 0.01 to 2.0 kg of active compound per ha.

[0422] The treatment of seeds generally requires active compound quantities of from 0.001 to 0.1 g, preferably from 0.01 to 0.05 g, per kilogram of seed.

[0423] For use in the protection of materials or stored products, the active compound application rate depends on the kind of application area and effect desired. Customary application rates in the protection of materials are, for example, from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active compound per cubic meter of treated material.

[0424] The compounds I can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the specific intended use; in any case, it should ensure fine and uniform distribution of the compound according to the invention.

[0425] The formulations are prepared in a known manner, e.g. by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants, it also being possible to use other organic solvents as auxiliary solvents if water is used as the diluent. Suitable auxiliaries for this purpose are essentially: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. mineral oil fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. finely divided silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates), and dispersants such as lignosulfite waste liquors and methylcellulose.

[0426] Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and alkali metal salts and alkaline earth metal salts thereof, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.

[0427] Suitable for preparing directly sprayable solutions, emulsions, pastes or oil dispersions are petroleum fractions having medium to high boiling points, such as kerosene or diesel oil, furthermore coal-tar oils and oils of plant or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, for example dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and water.

[0428] Powders, compositions for broadcasting and dusts can be prepared by mixing or jointly grinding the active substances with a solid carrier.

[0429] Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Solid carriers are, for example, mineral earths, such as silica gel, silicas, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

[0430] The formulations generally comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound. The active compounds are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to the NMR spectrum).

[0431] Examples of Formulations are:

[0432] I. 5 parts by weight of a compound according to the invention are thoroughly mixed with 95 parts by weight of finely divided kaolin. This affords a dusting composition comprising 5% by weight of the active compound.

[0433] II. 30 parts by weight of a compound according to the invention are thoroughly mixed with a mixture of 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel. This affords an active compound preparation having good adhesive properties (active compound content 23% by weight).

[0434] III. 10 parts by weight of a compound according to the invention are dissolved in a mixture comprising 90 parts by weight of xylene, 6 parts by weight of the addition product of 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-monoethanolamide, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil (active compound content 9% by weight).

[0435] IV. 20 parts by weight of a compound according to the invention are dissolved in a mixture comprising 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the addition product of 7 mol of ethylene oxide to 1 mol of isooctylphenol and 5 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil (active compound content 16% by weight).

[0436] V. 80 parts by weight of a compound according to the invention are mixed well with 3 parts by weight of the sodium salt of 45 diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel, and ground in a hammer mill (active compound content 80% by weight).

[0437] VI. 90 parts by weight of a compound according to the invention are mixed with 10 parts by weight of N-methyl-α-pyrrolidone, affording a solution which is suitable for use in the form of very small drops (active compound content 90% by weight).

[0438] VII. 20 parts by weight of a compound according to the invention are dissolved in a mixture comprising 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 mol of ethylene oxide to 1 mol of isooctylphenol and 10 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil. The solution is poured into 100 000 parts by weight of water and finely dispersed therein, affording an aqueous dispersion comprising 0.02% by weight of active compound.

[0439] VIII. 20 parts by weight of a compound according to the invention are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and ground in a hammer mill. The mixture is finely dispersed in 20 000 parts by weight of water, affording a spray liquor comprising 0.1% by weight of active compound.

[0440] The active compounds can be applied as such, in the form of their formulations or in the application forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusting compositions, compositions for broadcasting, or granules, by spraying, atomizing, dusting, broadcasting or watering. The application forms depend entirely on the intended uses; in any case, they should ensure the finest dispersion possible of the active compounds according to the invention.

[0441] Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders, oil dispersions) by addition of water. To prepare emulsions, pastes or oil dispersions, the substances can be homogenized in water as such or dissolved in an oil or solvent, by means of wetting agents, tackifiers, dispersants or emulsifiers. However, concentrates comprising active compound, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil which are suitable for dilution with water can also be prepared.

[0442] The active compound concentrations in the ready-to-use preparations can be varied over a relatively wide range. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.

[0443] It is also possible to use the active compounds with good success in the ultra-low-volume method (ULV), it being possible to apply formulations comprising more than 95% by weight of active compound or even the active compound without additives.

[0444] Oils of various types, herbicides, fungicides, other pesticides and bactericides can be added to the active compounds, if desired even immediately prior to application (tank mix). These agents can be added to the compositions according to the invention in a weight ratio of 1:10 to 10:1.

[0445] The compositions according to the invention in the use form as fungicides may also be present in combination with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. In many cases, a mixture of the compounds I, or of the compositions comprising them, in the use form as fungicides with other fungicides results in a broader fungicidal spectrum of activity.

[0446] The following list of fungicides in combination with which the compounds according to the invention can be used is intended to illustrate the possible combinations, but not to impose any limitation:

[0447] a sulfur, dithiocarbamates and their derivatives, such as iron(III) dimethyldithiocarbamate, zinc dimethyldithio-carbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediamine-bisdithiocarbamate, tetramethylthiuram disulfides, ammonia complex of zinc (N,N-ethylenebisdithiocarbamate), ammonia complex of zinc (N,N′-propylenebisdithiocarbamate), zinc (N,N′-propylenebisdithiocarbamate), N,N′-polypropylenebis-(thiocarbamoyl)disulfide;

[0448] nitro derivatives, such as dinitro-(1-methylheptyl)phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl 5-nitroisophthalate;

[0449] heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethyl phthalimidophosphonothioate, 5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo-[4,5-b]quinoxaline, methyl 1-(butylcarbamoyl)-2-benzimidazole-carbamate, 2-methoxycarbonylaminobenzimidazole, 2-(furyl-(2))-benzimidazole, 2-(thiazolyl-(4))-benzimidazole, N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloro-methylthiophthalimide,

[0450] N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfuric diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridine 2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethyl-furan-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide, N-cyclohexyl-2,5-dimethylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine 2,2,2-trichloroethyl acetal, piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)-formamide, 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-tri-chloroethane, 2,6-dimethyl-N-tridecylmorpholine or its salts, 2,6-dimethyl-N-cyclododecylmorpholine or its salts, N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethyl-morpholine, N-[3-(p-tert-butylphenyl)-2-methylpropyl]-piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole, 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole, N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N′-imidazolylurea, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol, (2RS, 3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4-triazole, α- (2-chlorophenyl) -α-(4-chlorophenyl) -5-pyrimidinemethanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis-(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene,

[0451] strobilurins, such as methyl E-methoxyimino[α-(o-tolyloxy)-o-tolyl]acetate, methyl E-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, methyl E-methoxy-imino[α-(2-phenoxyphenyl)lacetamide, methyl E-methoxyimino-[α-(2,5-dimethylphenoxy)-o-tolyl]acetamide, methyl E-2-{2-[(2-trifluoromethylpyrid-6-yl)oxymethyl]phenyl}-3-methoxyacrylate, methyl (E,E)-methoximino-{2-[1-(3-trifluoro-methylphenyl)ethylideneaminooxymethyl]phenyl}acetate, methyl N-(2-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl}phenyl)-N-methoxycarbamate,

[0452] anilinopyrimidines, such as N-(4,6-dimethylpyrimidin-2-yl)aniline, N-[4-methyl-6-(l-propynyl)pyrimidin-2-yl]aniline, N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline, phenylpyrroles, such as 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile,

[0453] cinnamamides, such as 3-(4-chlorophenyl)-3-(3,4-dimethoxy-phenyl)acryloylmorpholine,

[0454] and a variety of fungicides, such as dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide, hexachlorobenzene, methyl N-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate, DL-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)-alanine methyl ester, N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone, DL-N-(2,6-dimethylphenyl)-N-(phenyl-acetyl)alanine methyl ester, 5-methyl-5-vinyl-3-(3,5-dichloro-phenyl)-2,4-dioxo-1,3-oxazolidine, 3-(3,5-dichlorophenyl)-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione, 3-(3,5-dichlorophenyl)-1-isopropyl carbamoylhydantoin, N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano-[N-(ethylaminocarbonyl)-2-meth-oximino]acetamide, 1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole, 2,4-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)-benzhydryl alcohol, N-(3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine, 1-((bis-(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole.

Synthesis Examples

[0455] The procedures given in the synthesis examples below were used to obtain further compounds I by appropriate modification of the starting materials. The compounds obtained in this manner are listed in the tables which follow, together with physical data.

EXAMPLE 1 Preparation of 5-bromo-6,6′-dimethyl-2,2′, 3′, 4′-tetramethoxybenz-hydryl alcohol

[0456]

[0457] 2.36 g of 2,3,4-trimethoxy-6-methylbromobenzene and 0.32 g of agnesium turnings were initially charged in 5 ml of anhydrous tetrahydrofuran, 0.57 ml of 1,2-dibromoethane was added and the reaction mixture was heated at reflux temperature for about 40 min. After cooling to 30° C., 1.40 g of 5-bromo-2-methoxy-6-methylbenzaldehyde were added dropwise, and the solution was stirred for about two hours. Water/2N hydrochloric acid (1/1) was added, the aqueous phase was extracted with ethyl acetate, the organic phases were washed with water and dried and the solvent was distilled off, and the residue was then purified by column chromatography (mobile phase petroleum ether/ethyl acetate 85/5). 1.5 g of the title compound were isolated as a violet viscous oil.

EXAMPLE 2 Preparation of 2,5-dichloro-6,6′-dimethyl-2′, 3′, 4′-trimethoxy-benzhydryl alcohol

[0458]

[0459] Under protective gas conditions, at about −78° C. , 1 ml of a 1-molar solution of LiAlH₄ in tetrahydrofuran was added dropwise to a solution of 0.37 g of 2,5-dichloro-6,6′-dimethyl-2′, 3′, 4′-trimethoxybenzophenone in 20 ml of anhydrous tetrahydrofuran, and the mixture was stirred for about 1 hour. At 20-25° C. , sat. NaHCO₃ solution was added to the reaction solution, the solution was extracted with ethyl acetate and the organic phase was washed with water and sat. NaCl solution and dried, and the solvent was then distilled off. The residue gave, after purification by column chromatography (mobile phase: ethyl acetate/cyclohexane 1:9), 150 mg of the title compound as a yellow viscous oil.

EXAMPLE 3 Preparation of 5-chloro-2-hydroxy-6,6′-dimethyl-2′, 3′, 4′-trimethoxybenzhydryl alcohol

[0460]

[0461] At −20° C. , under an atmosphere of protective gas, 3 mmol of a 1-molar solution of LiAlH₄ in tetrahydrofuran (THF) were added dropwise to a solution of 0.86 g of 5-chloro-2-hydroxy-6,6′-dimethyl-2′, 3′, 4′-trimethoxybenzophenone in 10 ml of anhydrous THF. The reaction mixture was warmed to room temperature and then admixed with ice water, acidified with dilute hydrochloric acid and extracted with ethyl acetate. The combined organic phases were washed with sat. NaCl solution, dried and purified by column chromatography (mobile phase: ethyl acetate/cyclohexane 3:7). This gave 0.46 mg of the title compound as a white solid of m.p. 140-142° C. TABLE I

phys. data No. R¹ (R²)_(n) R³ R⁴ R⁵ R⁵ (m.p.[° C.]) I-1 OCH₃ 5-Br CH₃ CH₃ OCH₃ OCH₃ oil I-2 Cl 5-Cl CH₃ CH₃ OCH₃ OCH₃ oil I-3 OH 5-Cl CH₃ CH₃ OCH₃ OCH₃ 140-142

Examples of the Activity Against Harmful Fungi

[0462] The fungicidal activity of the compounds of the formula I was demonstrated by the following experiments:

[0463] The active compounds were formulated, separately or together, as a 10% strength emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN (Lutensol® AP6, wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight of Wettol® EM (nonionic emulsifier based on ethoxylated castor oil) and diluted with water to the desired concentration.

[0464] After conclusion of the tests, in each case the lowest concentration at which the compounds still caused 80-100% inhibition in comparison to untreated controls (activity 45 threshold or minimum concentration) was determined.

Use Example 1—Activity Against Mildew of Wheat

[0465] Leaves of potted wheat seedlings cv. “Kanzler” were sprayed to runoff point with an aqueous preparation of active compound which had been prepared from a stock solution made of 10% of active compound, 63% of cyclohexanone and 27% of emulsifier. 24 hours after the spray coating had dried on, the leaves were dusted with spores of mildew of wheat (Erysiphe graminis forma specialis tritici). The test plants were then placed in a greenhouse at 20-24° C. and 60-90% rel. atmospheric humidity. After 7 days, the extent of the mildew development was determined visually as % infection of the total leaf area.

[0466] In this test, the plants which had been treated with 4 or 16 ppm of the active compounds I-1, I-2 and 1-3 showed an infection of in each case at most 30%, whereas the untreated plants were infected to 90%. 

We claim:
 1. A benzhydryl derivative of the formula I,

where the index and the variables are as defined below: X is oxygen or sulfur; R¹ , R³ are halogen, cyano, nitro, hydroxyl, mercapto, amino, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy, C₂-C₆-alkenyloxy, C₂-C₆-alkynyloxy, C₁-C₆-alkylcarbonyloxy, formyloxy, C₁-C₆-alkylthio, C₂-C₆-alkenylthio, C₂-C₆-alkynylthio, C₁-C₆-alkylamino, di-C₁-C₆-alkylamino, C₁-C₆-alkylcarbonyl or formyl, where the carbon atoms in the radicals mentioned may be partially or fully halogenated; R² is halogen, cyano, nitro, hydroxyl, mercapto, amino, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C₆-haloalkoxy, where the groups R² may be different if n=2; R⁴ is C₁-C₆-alkyl, C₂-C₆-alkenyl or C₂-C₆-alkynyl, where the carbon atoms in these radicals may be unsubstituted or partially or fully halogenated; R⁵, R⁶ are hydroxyl, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₁-C₆-alkoxy, C₂-C₆-alkenyloxy, C₁-C₆-haloalkoxy, C₂-C₆-haloalkenyloxy, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyl-C₁-C₃-alkyl, C₃-C₈-cycloalkoxy or C₃-C₈-cycloalkyl-C₁-C₃-alkoxy; n is 0, 1 or
 2. 2. A compound of the formula I as claimed in claim 1 where X is oxygen.
 3. A compound of the formula I as claimed in claim 1 where the variables are as defined below: R¹, R³ independently of one another are halogen, hydroxyl, amino, mercapto, nitro, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylcarbonyloxy, C₁-C₆-haloalkylcarbonyloxy, C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, C₁-C₆-alkylcarbonyl or C₁-C₆-haloalkylcarbonyl.
 4. A compound of the formula I as claimed in claim 1 where R² is halogen, hydroxyl, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy or C₁-C₆-haloalkoxy.
 5. A compound of the formula I as claimed in claim 1 where R⁴ is C₁-C₆-alkyl or C₁-C₆-haloalkyl.
 6. A compound of the formula I as claimed in claim 1 where R⁵, R⁶ are hydroxyl, C₁-C₆-alkoxy, C₂-C₆-alkenyloxy, C₁-C₆-haloalkoxy or C₂-C₆-haloalkenyloxy.
 7. A compound of the formula I as claimed in claim 1, where the variables are as defined below: R¹, R³ are halogen, hydroxyl, amino, mercapto, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy or C₁-C₆-alkylcarbonyl; R² is halogen, hydroxyl, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy or C₁-C₆-haloalkoxy; R⁴ is methyl; R⁵, R⁶ are C₁-C₆-alkoxy; n is 0 or
 1. 8. A process for preparing compounds of the formula I as claimed in claim 1 in which X is oxygen, by reacting aldehydes of the formula II,

where the variables R¹, R², R³ and n are as defined for formula I and may be protected by a protective group Q which is removed after the reaction, with halobenzene derivatives of the formula III,

where the variables R⁴, R⁵ and R⁶ are as defined for formula I and A is halogen, and A is converted, in an intermediate step, into a group B, where B is a suitable metal or a suitable halometal group.
 9. A process for preparing compounds of the formula I as claimed in claim 1 in which X is oxygen, by reduction of benzophenone derivatives of the formula IV,

where the variables are as defined for formula I or denote a group which, after the reaction, can be converted into these radicals using hydrides or by catalytic reduction with H₂.
 10. A composition suitable for controlling phytopathogenic harmful fungi, which comprises a solid or liquid carrier and a compound of the formula I as claimed in claim
 1. 11. A method for controlling phytopathogenic fungi, which comprises treating the fungi or the materials, plants, the soil or the seed to be protected against fungal attack with an effective amount of a compound of the formula I as claimed in claim
 1. 